WO2020075508A1

WO2020075508A1 - Liquid crystal composition and liquid crystal display element

Info

Publication number: WO2020075508A1
Application number: PCT/JP2019/037806
Authority: WO
Inventors: 雄一井ノ上; 純一間宮; 淳子山本; 正臣木村
Original assignee: Dic株式会社
Priority date: 2018-10-11
Filing date: 2019-09-26
Publication date: 2020-04-16
Also published as: JPWO2020075508A1; CN112437802A; JP6787527B2; TW202028436A

Abstract

Provided are: a liquid crystal composition in which a large amount of polymerizable monomer is dissolved, the liquid crystal composition capable of forming a pre-tilt angle in a shorter time by sufficiently increasing the rate of polymerization thereof; and a liquid crystal display which uses a related liquid crystal composition, has a sufficient pre-tilt angle , has little or no change in pre-tilt angle, and is excellent in terms of voltage holding ratio (VHR) and response performance. A liquid crystal composition according to the present invention is characterized by containing: a liquid crystal molecule; a polymerizable monomer A which has a mesogenic skeleton and at least two polymerizable groups bonded to the mesogenic skeleton, wherein all of the polymerizable groups are directly bonded to the mesogenic skeleton; and a polymerizable monomer B which has a mesogenic skeleton and at least two polymerizable groups bonded to the mesogenic skeleton, wherein all of the polymerizable groups are bonded to the mesogenic skeleton via spacer groups.

Description

Liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal composition and a liquid crystal display device.

In order to improve the characteristics of a liquid crystal display device, a polymerizable monomer such as PSA (Polymer Sustained Alignment) is mixed in the liquid crystal composition constituting the liquid crystal layer to control the alignment state of liquid crystal molecules. In some cases (see Patent Documents 1 to 5, for example).

If the polymerizable monomer does not have a spacer group in the molecule, the polymer obtained by polymerizing the polymerizable monomer becomes rigid. Therefore, it is possible to reduce the occurrence of IS (Image Sticking: image sticking) in the liquid crystal display element. However, such a polymerizable monomer may have low solubility in the liquid crystal composition.

U.S. Patent Application Publication No. 2010/0124623 Japanese Patent No. 6087815 International Publication No. 2017/008884 Japanese Patent Publication No. 2015-513577 U.S. Patent No. 9139775

An object of the present invention is to dissolve a large amount of a polymerizable monomer, and to sufficiently increase the polymerization rate thereof to form a pretilt angle in a shorter time, and a liquid crystal composition containing such a liquid crystal composition. It is an object of the present invention to provide a liquid crystal display element that has a large pretilt angle, has little or no change in the pretilt angle, and has excellent voltage holding ratio (VHR) and response performance.

Such an object is achieved by the present invention described in (1) to (13) below.

(1) Liquid crystal molecules,
A polymerizable monomer A having a mesogen skeleton and at least two polymerizable groups bonded to the mesogen skeleton, all of the polymerizable groups being directly bonded to the mesogen skeleton;
A polymerizable monomer B having a mesogenic skeleton and at least two polymerizable groups bonded to the mesogenic skeleton, all of the polymerizable groups being bonded to the mesogenic skeleton via a spacer group. A liquid crystal composition comprising:

(2) The liquid crystal composition according to (1) above, wherein in the polymerizable monomer A, the two polymerizable groups are bonded to substantially symmetrical positions at both ends in the long axis direction of the mesogenic skeleton.

(3) The liquid crystal composition according to the above (1) or (2), wherein in the polymerizable monomer A, the mesogen skeleton has 2 to 4 ring structures.

(4) The liquid crystal composition according to (3), wherein in the polymerizable monomer A, the mesogen skeleton further includes the following substituent K ^i1A bonded to the ring structure.

The substituent K ^i1A is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched chain. Represents a cyanated alkyl group having 1 to 40 carbon atoms, or a linear or branched alkoxy group having 1 to 40 carbon atoms.
(Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X ⁱ¹ ) ^-and / ^or- (CH-CN)-, and the secondary carbon atom in the alkyl group is The carbon atom is -C (= CH ₂ )-, -C (= CHR ⁱ³ )-, -C (= CR ⁱ³ ₂ )-, -CH = CH-, -C≡C so that the oxygen atom is not directly adjacent. It may be substituted with —, —O—, —NH—, —COO— or —OCO—, and the end of the alkyl group may be substituted with OH, NH ₂ or CN, wherein X ⁱ¹ is , An oxygen atom, a sulfur atom, NH or NR ⁱ³ , and R ⁱ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms (provided that the secondary carbon atom in the alkyl group is , Substituted with -O-, -CH = CH- or -C≡C- so that oxygen atoms are not directly adjacent May be done.).)

(5) The liquid crystal composition according to any one of (1) to (4) above, wherein in the polymerizable monomer B, the mesogen skeleton includes 2 to 4 ring structures.

(6) The liquid crystal composition according to (5) above, wherein in the polymerizable monomer B, the 2 to 4 ring structures in the mesogen skeleton form a linked polycyclic structure.

(7) The liquid crystal composition according to the above (6), wherein in the polymerizable monomer B, the mesogenic skeleton further includes the following substituent K ^i1B bonded to the ring structure.

The substituent K ^i1B is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched group. Represents a cyanated alkyl group having 1 to 40 carbon atoms, or a linear or branched alkoxy group having 1 to 40 carbon atoms.
(Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X ⁱ¹ ) ^-and / ^or- (CH-CN)-, and the secondary carbon atom in the alkyl group is The carbon atom is -C (= CH ₂ )-, -C (= CHR ⁱ³ )-, -C (= CR ⁱ³ ₂ )-, -CH = CH-, -C≡C so that the oxygen atom is not directly adjacent. It may be substituted with-, -O-, -NH-, -COO- or -OCO-, the hydrogen atom in the alkyl group may be substituted with P-Sp-, and the terminal of the alkyl group is , OH, NH ₂ or CN, wherein X ⁱ¹ represents an oxygen atom, a sulfur atom, NH or NR ⁱ³ , and R ⁱ³ has a linear or branched carbon atom number of 1 to 20 represents an alkyl group (provided that the secondary carbon atom in this alkyl group is directly linked to the oxygen atom). It may be substituted with -O-, -CH = CH- or -C≡C- so as not to be adjacent to each other.), P represents a polymerizable group, and Sp represents a spacer group.)

(8) The amount of the polymerizable monomer A based on the total amount of the polymerizable monomer A and the polymerizable monomer B is 25 to 75% by mass, as described in any one of (1) to (7) above. Liquid crystal composition.

(9) The total amount of the polymerizable monomer A and the polymerizable monomer B contained in the liquid crystal composition is 0.1 to 3 parts by mass with respect to 100 parts by mass of the liquid crystal molecule. ) -The liquid crystal composition according to any one of (8).

(10) It is characterized by comprising two substrates and a liquid crystal layer provided between the two substrates and containing the liquid crystal composition according to any one of the above (1) to (9). Liquid crystal display device.

(11) The liquid crystal display element according to (10), wherein the liquid crystal layer contains a polymerized product of the polymerizable monomer A and the polymerizable monomer B.

(12) The liquid crystal display element according to (10) or (11) above, which is for driving an active matrix.

(13) The liquid crystal display element according to any one of (10) to (12) above, which is a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type.

According to the present invention, by using the polymerizable monomer having a spacer group and the polymerizable monomer having no spacer group in combination, a large amount of the polymerizable monomer is dissolved, and by sufficiently increasing the polymerization rate, A liquid crystal composition capable of forming a pretilt angle in a short time can be obtained. Further, by using such a liquid crystal composition, a liquid crystal display element having a sufficient pretilt angle, a change in the pretilt angle that is not generated or an extremely small amount, and an excellent voltage holding ratio (VHR) and response performance can be obtained.

It is a figure which shows one Embodiment of a liquid crystal display element typically. It is the top view which expanded the area | region enclosed by the I line in FIG.

Hereinafter, the liquid crystal composition and the liquid crystal display device of the present invention will be described in detail based on preferred embodiments.

(Liquid crystal composition)
It contains a liquid crystal molecule, a polymerizable monomer A in which all the polymerizable groups are directly bonded to the mesogenic skeleton, and a polymerizable monomer B in which all the polymerizable groups are bonded to the mesogenic skeleton via a spacer group.

The polymerizable monomer A in which the polymerizable group is directly bonded to the mesogenic skeleton without a spacer group is generally rigid and therefore has low solubility in the liquid crystal composition.

On the other hand, the polymerizable monomer B in which the polymerizable group is bonded to the mesogenic skeleton via the spacer group is flexible due to the presence of the spacer group and has high solubility in the liquid crystal composition.

In the present invention, the amount of the polymerizable monomer A contained in the liquid crystal composition can be increased by using the polymerizable monomer A and the polymerizable monomer B together. Therefore, a liquid crystal composition in which the polymerizable monomer containing a large amount of the polymerizable monomer A is dissolved can be obtained. Since the liquid crystal composition can complete the polymerization reaction in a shorter time, the energy cost can be optimized.

Further, the liquid crystal composition of the present invention has a low viscosity (η) and a small rotational viscosity (γ1) without lowering the refractive index anisotropy (Δn) and the nematic phase-isotropic liquid phase transition temperature (Tni). ) And a large bend elastic constant (K33).

From the above, the liquid crystal display device (liquid crystal layer) using the liquid crystal composition of the present invention can impart a sufficient pretilt angle to liquid crystal molecules and reduce the residual amount of the polymerizable monomer. You can also As a result, the liquid crystal display element exhibits a high voltage holding ratio (VHR) and a high-speed response, and exhibits excellent display quality in which alignment defects, IS (image sticking), etc. are prevented or suppressed.

((Polymerizable monomer A))
The polymerizable monomer A has a mesogenic skeleton and at least two polymerizable groups bonded to the mesogenic skeleton. And all of the polymerizable groups are directly bonded to the mesogenic skeleton.

The mesogenic skeleton preferably has 2 to 4 ring structures, and more preferably 2 to 3 ring structures. By providing the mesogenic skeleton having such a number of ring structures, it is possible to further enhance the function of providing the polymerizable monomer A with the bretil angle to the liquid crystal molecules.

Specific examples of the mesogenic skeleton include the following formula (B ⁱ¹¹ ), formula (B ⁱ¹² ) or formula (B ⁱ⁴¹ ).

One or more hydrogen atoms in the ring structure may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms.

The polymerizable monomer A has at least two polymerizable groups. By polymerizing the polymerizable groups of the polymerizable monomer A and the polymerizable monomer B with each other, the polymerized product of the polymerizable monomer A and the polymerizable monomer B can be firmly fixed to the substrate, and at the same time, the holding power of liquid crystal molecules can be increased. It can also be increased. As a result, separation of the liquid crystal layer from the substrate can be prevented or suppressed. In addition, the pretilt angle imparting force for the liquid crystal molecules can be improved.

The number of polymerizable groups may be two, but may be three or more. By having two or more polymerizable groups, the crosslink density of the polymer can be increased. Therefore, these can be more firmly fixed to the substrate, and the holding force of the liquid crystal molecules and the pretilt angle imparting force can be further increased.

Such a polymerizable group is selected, for example, from the group represented by the following general formulas (P-1) to (P-13).

(In the formula, the black dot at the right end represents a bond.)

Since these polymerizable groups are highly reactive, they can be polymerized sufficiently and reliably even with relatively low energy (for example, light energy and heat energy). Therefore, when the polymerizable monomer A and the polymerizable monomer B are polymerized, it is possible to prevent or suppress the liquid crystal molecules from being adversely affected and deteriorated.

Among these, the polymerizable group is preferably a group represented by formula (P-1) to formula (P-3), and a group represented by formula (P-1) (acryloyl group) or formula (P-2) Group represented by () (methacryloyl group) is more preferable.

The two or more polymerizable groups contained in the polymerizable monomer A may be the same or different from each other.

Moreover, it is preferable that the two polymerizable groups are bonded to substantially symmetrical positions at both ends in the long axis direction of the mesogenic skeleton. As a result, the effect of giving the pretilt angle to the liquid crystal molecules is further enhanced.

Examples of the polymerizable monomer A as described above include compounds represented by the following general formulas (i-1-1) to (i-4-14).

In the formula, P ⁱ¹¹ , P ⁱ¹² , P ⁱ²¹ , P ⁱ²² , P ⁱ⁴¹ and P ⁱ⁴² each independently represent the above polymerizable group.

The mesogenic skeleton has a substituent K ^i1A which is bonded to the ring structure in place of or together with the substituents in the general formulas (i-1-1) to (i-4-14). May be.

The substituent K ^i1A is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched chain. Represents a cyanated alkyl group having 1 to 40 carbon atoms or a linear or branched alkoxy group having 1 to 40 carbon atoms, which is a halogen atom, or a linear or branched carbon atom having 3 to 40 alkyl group, linear or branched halogenated alkyl group having 3 to 40 carbon atoms, linear or branched cyanated alkyl group having 3 to 40 carbon atoms, or linear or branched Is preferably an alkoxy group having 3 to 40 carbon atoms, and is a linear alkyl group having 3 to 40 carbon atoms, a linear halogenated alkyl group having 3 to 40 carbon atoms, or a linear carbon atom. Number 3 ~ A 40-alkoxy group is preferable, a linear alkyl group having 3 to 18 carbon atoms or a linear alkoxy group having 3 to 18 carbon atoms is preferable, and a linear alkyl group having 3 to 12 carbon atoms. Alternatively, a linear alkoxy group having 3 to 12 carbon atoms is preferable, and a linear alkyl group having 3 to 8 carbon atoms or a linear alkoxy group having 3 to 8 carbon atoms is preferable.

Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X ⁱ¹ ) ^-and / ^or- (CH-CN)-, and the secondary carbon atom in the alkyl group is Atoms are -C (= CH ₂ )-, -C (= CHR ⁱ³ )-, -C (= CR ⁱ³ ₂ )-, -CH = CH-, -C≡C- so that oxygen atoms are not directly adjacent to each other. , —O—, —NH—, —COO— or —OCO—, and the end of the alkyl group may be substituted with OH, NH ₂ or CN.

In the formula, X ⁱ¹ represents an oxygen atom, a sulfur atom, NH or NR ⁱ³ , and R ⁱ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms (provided that, in this alkyl group, The secondary carbon atom may be substituted with —O—, —CH═CH— or —C≡C— so that the oxygen atom is not directly adjacent.)

When the polymerizable monomer A has a mesogenic skeleton ^{including the} substituent K ^i1A , it is possible to more reliably impart a sufficient pretilt angle to liquid crystal molecules and make it more difficult for the pretilt angle to change.

((Polymerizable monomer B))
The polymerizable monomer B has a mesogenic skeleton and at least two polymerizable groups bonded to this mesogenic skeleton. Then, all of the polymerizable groups are bonded to the mesogenic skeleton via a spacer group.

By using the polymerizable monomer B together, the amount of the polymerizable monomer A contained in the liquid crystal composition can be increased.

Here, as the spacer group, for example, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO—, —CF ₂ O—, _{_{_{-OCF 2 -, - CH = CHCOO}}} -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3 ) = CH—, —CH ₂ —CH (CH ₃ ) COO—, —OCOCH (CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—, or a branched or linear carbon atom number of 1 to 20 (However, one or two or more —CH ₂ — which are not adjacent to each other in the alkylene group may be substituted with —O—, —COO— or —OCO—).

Among them, the spacer group is preferably a branched or linear alkylene group having 2 to 15 carbon atoms, and more preferably a branched or linear alkylene group having 3 to 10 carbon atoms. Since the polymerizable monomer B having such a spacer group has high molecular mobility, a larger amount of the polymerizable monomer A can be dissolved in the liquid crystal composition.

The mesogenic skeleton preferably has 2 to 4 ring structures, and more preferably 2 to 3 ring structures. By providing the mesogenic skeleton having such a number of ring structures, it is possible to further enhance the function of the polymerizable monomer B to impart the bretil angle to the liquid crystal molecules.

The plurality of ring structures contained in the mesogen skeleton may form a condensed polycyclic structure, but it is preferable that the ring structures form a linked polycyclic structure in which the ring structures are linked (bonded) by a single bond. This further enhances the mobility of the molecules of the polymerizable monomer B.

The polymerizable monomer B has at least two polymerizable groups. By polymerizing the polymerizable groups of the polymerizable monomer A and the polymerizable monomer B with each other, the polymerized product of the polymerizable monomer A and the polymerizable monomer B can be firmly fixed to the substrate, and at the same time, the holding power of liquid crystal molecules can be increased. It can also be increased. As a result, the pretilt angle imparting force can be improved.

Such a polymerizable group is selected, for example, from the group represented by the above general formulas (P-1) to (P-13). Among these, the polymerizable group is preferably a group represented by formula (P-1) to formula (P-3), and a group represented by formula (P-1) (acryloyl group) or formula (P-2) Group represented by () (methacryloyl group) is more preferable.

The two or more polymerizable groups contained in the polymerizable monomer B may be the same or different from each other.

The polymerizable monomer B preferably contains, for example, at least one selected from the compounds represented by the following general formula (i-6-1).

In the formula, X represents a ring structure (aliphatic ring structure or aromatic ring structure), P represents a polymerizable group, Sp represents a spacer group, a represents an integer of 0 to 2, and m , N, and o each independently represent an integer of 0 to 3, and m + n + o is 2 or more.

The polymerizable group P and the spacer group Sp are the same as the groups described above.

Further, the mesogenic skeleton may further include a substituent K ^i1B bonded to the ring structure X.

The substituent K ^i1B is a halogen atom, a linear or branched alkyl group having 3 to 40 carbon atoms, a linear or branched halogenated alkyl group having 3 to 40 carbon atoms, a linear or branched group. Represents a cyanated alkyl group having 3 to 40 carbon atoms, or a linear or branched alkoxy group having 3 to 40 carbon atoms.

Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X ⁱ¹ ) ^-and / ^or- (CH-CN)-, and the secondary carbon atom in the alkyl group is Is -C (= CH ₂ )-, -C (= CHR ⁱ³ )-, -C (= CR ⁱ³ ₂ )-, -CH = CH-, -C≡C-, so that oxygen atoms are not directly adjacent to each other. It may be substituted with —O—, —NH—, —COO— or —OCO—, the hydrogen atom in the alkyl group may be substituted with P—Sp—, and the end of the alkyl group may be OH, NH. ₂ or CN may be substituted.

In the formula, X ⁱ¹ represents an oxygen atom, a sulfur atom, NH or NR ⁱ³ , and R ⁱ³ represents a linear or branched alkyl group having 1 to 20 carbon atoms (provided that in this alkyl group, The secondary carbon atom may be substituted with —O—, —CH═CH— or —C≡C— so that oxygen atoms are not directly adjacent to each other.), P represents a polymerizable group and Sp represents , Represents a spacer group. )
Since the polymerizable monomer B has a mesogenic skeleton including the substituent K ^i1B , it is possible to more reliably impart a sufficient pretilt angle to liquid crystal molecules and make it more difficult for the pretilt angle to change.

The substituent K ^i1B is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched group. Represents a cyanated alkyl group having 1 to 40 carbon atoms or a linear or branched alkoxy group having 1 to 40 carbon atoms, which is a halogen atom, or a linear or branched carbon atom having 3 to 40 alkyl group, linear or branched halogenated alkyl group having 3 to 40 carbon atoms, linear or branched cyanated alkyl group having 3 to 40 carbon atoms, or linear or branched Is preferably an alkoxy group having 3 to 40 carbon atoms, and is a linear alkyl group having 3 to 40 carbon atoms, a linear halogenated alkyl group having 3 to 40 carbon atoms, or a linear carbon atom. Number 3 ~ A 40-alkoxy group is preferable, a linear alkyl group having 3 to 18 carbon atoms or a linear alkoxy group having 3 to 18 carbon atoms is preferable, and a linear alkyl group having 3 to 12 carbon atoms. Alternatively, a linear alkoxy group having 3 to 12 carbon atoms is preferable, and a linear alkyl group having 3 to 8 carbon atoms or a linear alkoxy group having 3 to 8 carbon atoms is preferable.

As the polymerizable monomer B, a compound having a spacer group between the mesogenic skeleton and each polymerizable group in the above general formulas (i-1-1) to (i-4-14) (that is, two polymerizable monomers) is used. The functional group may be bonded to both ends of the mesogen skeleton in the longitudinal direction at substantially symmetrical positions), and a compound represented by the following formulas (i-6-11) to (i-6-13) ( That is, a compound in which two polymerizable groups are unevenly distributed and bonded at one end in the long axis direction of the mesogenic skeleton) may be used.

The latter polymerizable monomer B is also preferable because it can act to assist the alignment control of liquid crystal molecules.

The amount of the polymerizable monomer A based on the total amount of the polymerizable monomer A and the polymerizable monomer B is preferably about 25 to 75% by mass, more preferably about 40 to 60% by mass. By using the polymerizable monomer A and the polymerizable monomer B in such a ratio, the pretilt angle imparted to the liquid crystal molecules can be further increased, and the occurrence of IS can be preferably prevented or suppressed.

The total amount of the polymerizable monomer A and the polymerizable monomer B contained in the liquid crystal composition is preferably about 0.1 to 3 parts by mass, and 0.2 to 2 parts by mass based on 100 parts by mass of the liquid crystal molecule. It is more preferable that the amount is about parts by mass. By setting the total amount of the polymerizable monomer A and the polymerizable monomer B in the above range, excellent VHR and high-speed response can be maintained.

((Liquid crystal molecule))
The liquid crystal molecule preferably contains at least one of the compounds represented by the general formulas (N-1) to (N-3).

In the formula, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, but any 1 Or two or more non-adjacent —CH ₂ — are each independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. Good.

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently,
(A) 1,4-cyclohexylene group (any one or two or more non-adjacent —CH ₂ — present in the group may be substituted with —O—),
(B) a 1,4-phenylene group (any one or two or more non-adjacent -CH = present in the group may be substituted with -N =),
(C) a naphthalene-2,6-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or a decahydronaphthalene-2,6-diyl group (any one present in the group) Or two or more -CH = which are not adjacent to each other may be substituted by -N =), and (d) represents a group selected from the group consisting of 1,4-cyclohexenylene groups. The group (a), group (b), group (c) and group (d) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom.

Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH _2. O-, -COO-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C- Represent

X ^N21 represents a hydrogen atom or a fluorine atom.

T ^N31 represents —CH ₂ — or an oxygen atom.

n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, and n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are respectively Independently, 1, 2 or 3, and when there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different.

R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms. Or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or It is more preferably an alkenyloxy group having 2 to 5 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and having 2 to 5 carbon atoms. An alkyl group or an alkenyl group having 2 to 3 carbon atoms is particularly preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is most preferable.

When they are bonded to a ring structure which is a benzene ring (aromatic ring), they are a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms. Alternatively, it is preferably an alkenyl group having 4 to 5 carbon atoms, and when it is bonded to a saturated ring structure such as a cyclohexane ring, a pyran ring or a dioxane ring, a linear alkyl group having 1 to 5 carbon atoms is used. A group, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms is preferable. In order to stabilize the nematic phase, it is preferable that the number of carbon atoms (the total number of carbon atoms and the number of oxygen atoms when oxygen atoms are contained) be 5 or less. It is also preferably chain-like.

The alkenyl group is preferably selected from the groups represented by any of the following formulas (R1) to (R5).

The black dots in each formula represent carbon atoms in the ring structure.

Each of A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 is preferably aromatic when it is required to increase Δn, in order to improve the response speed. It is preferably aliphatic.

Specifically, A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro group. -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-cyclohexene Cenylene 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, It is preferably a 2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably one of the groups of the following Chemical formula 13, and a trans-1,4-cyclohexylene group. More preferably, it is a 1,4-cyclohexenylene group or a 1,4-phenylene group.

^{^{^{^{Z N11, Z N12, Z N21}}}} , Z N22, Z N31 and ^{Z N32} are each _{_{independently, -CH 2 O -, - CF}} 2 O -, - CH 2 CH 2 -, - CF 2 CF 2 - or it is preferably a single _{_{bond, -CH 2 O -, - CH}} 2 CH 2 - or more preferably a single bond, _-CH 2 O-or a single bond is more preferable.

X ^N21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2. Specifically, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, a combination in which n ^N11 is 1 and n ^N12 is 1, and n ^N21 is 1 and n ^N22 is 0, n ^N21 is 2 and n ^N22 is 0, n ^N31 is 1 and n ^N32 is 0, n ^N31 is 2 and n ^N32 is 0 Certain combinations are preferred.

The amounts of the compounds represented by the general formulas (N-1) to (N-3) contained in the liquid crystal composition are preferably as follows. That is, the preferable lower limit value is 1% by mass, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass. % And 80% by mass. On the other hand, the preferable upper limit values are 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass and 20% by mass.

When the viscosity (η) of the liquid crystal composition is kept low and the response speed is increased, the amount of the compounds represented by the general formulas (N-1) to (N-3) has a low lower limit and a low upper limit. Is preferred. Further, in order to maintain the nematic phase-isotropic liquid phase transition temperature (Tni) of the liquid crystal composition at a high level and improve the temperature stability, the lower limit and the lower limit of the amount are preferably low. When the dielectric anisotropy (Δε) of the liquid crystal composition is increased in order to keep the driving voltage of the liquid crystal display element low, the lower limit and the upper limit of the amount are preferably high.

Examples of the compound represented by the general formula (N-1) include compounds represented by the following general formulas (N-1a) to (N-1g).

^{Wherein, R N11} and ^{R N12} are the same meanings as ^{R N11} and ^{R N12} in the general formula (N-1).

^nNa11 represents 0 or 1.

n ^Nb11 represents 1 or 2.

n ^Nc11 represents 0 or 1.

n ^Nd11 represents 1 or 2.

n ^Ne11 represents 1 or 2.

n ^Nf12 represents 1 or 2.

n ^Ng11 represents 1 or 2.

A ^Ne11 represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group, but at least one represents a 1,4-cyclohexenylene group.

Z ^Ne11 represents a single bond or an ethylene group, but at least one represents an ethylene group.

However, when a plurality of A ^Ne11 , Z ^Ne11 and / or A ^Ng11 are present, they may be the same or different.

More specifically, the compound represented by the general formula (N-1) is preferably selected from compounds represented by the following general formulas (N-1-1) to (N-1-21).

The compound represented by the general formula (N-1-1) is the following compound.

In the formula, R ^N111 and R ^N112 each independently have the same meaning as R ^N11 and R ^N12 in formula (N-1).

R ^N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably a propyl group, a pentyl group or a vinyl group.

R ^N112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a butoxy group. .

The compound represented by the general formula (N-1-1) can be used alone or in combination of two or more.

The type of compound that can be used in combination is not particularly limited, but is appropriately selected according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence.

The types of compounds used are, for example, one type, two types, three types, four types, and five or more types in one embodiment of the present invention.

The amount of the compound represented by the general formula (N-1-1) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when set high, and when Tni is important, the effect is high when set low. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

Its preferable lower limit value is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass, It is 35 mass%. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass. %, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.

Further, the compound represented by the general formula (N-1-1) is preferably selected from compounds represented by the following formulas (N-1-1.1) to (N-1-1.25). Are more preferably selected from compounds represented by the following formulas (N-1-1.1) to (N-1-1.4), and the following formulas (N-1-1.1) and (N- More preferably, it is selected from the compounds represented by 1-1.3).

The compounds represented by the formulas (N-1-1.1) to (N-1-1.25) can be used alone or in combination of two or more.

The amounts of the compounds represented by the formulas (N-1-1.1) to (N-1-1.25) contained in the liquid crystal composition, alone or in combination, are preferably as follows. That is, the preferable lower limit value is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass. % And 35% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass. %, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.

The compound represented by the general formula (N-1-2) is the following compound.

In the formula, R ^N121 and R ^N122 each independently have the same meaning as R ^N11 and R ^N12 in formula (N-1).

R ^N121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group, a butyl group or a pentyl group.

R ^N122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a methyl group, a propyl group, a methoxy group, an ethoxy group. Alternatively, it is more preferably a propoxy group.

The compound represented by the general formula (N-1-2) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-2) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when the value is set low, and the effect is high when the value is emphasized when Tni is important. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferred lower limit values are 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass, 35% by mass, 37% by mass, 40% by mass and 42% by mass. On the other hand, the preferable upper limit values are 50% by mass, 48% by mass, 45% by mass, 43% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass. %, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%.

Further, the compound represented by the general formula (N-1-2) is preferably selected from the compounds represented by the following formulas (N-1-2.1) to (N-1-2.25). , Formulas (N-1-2.3) to (N-1-2.7), formulas (N-1-2.10), formulas (N-1-2.11), formulas (N-1-) It is more preferred to be selected from the compounds represented by 2.13) and the formula (N-1-2.20).

The compounds represented by the general formula (N-1-2) are represented by the formulas (N-1-2.3) to (N-1-2.7) when the improvement of Δε is important. is preferably selected from _compounds, when emphasizing improvements in _{T ni} of the formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2 .13), and when the improvement in response speed is important, the compound represented by the formula (N-1-2.20) is preferable.

The compounds represented by the formulas (N-1-2.1) to (N-1-2.25) can be used alone or in combination of two or more.

The amount of the compounds represented by formulas (N-1-2.1) to (N-1-2.25) contained in the liquid crystal composition, alone or in combination, is preferably as follows. That is, the preferable lower limit value is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass. % And 35% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass. %, 15 mass%, 13 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 3 mass%.

The compound represented by the general formula (N-1-3) is the following compound.

In the formula, R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.

R ^N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and is 1-propenyl group, ethoxy group, propoxy group or It is more preferably a butoxy group.

The compound represented by the general formula (N-1-3) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-3) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferable lower limit values are 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

Further, the compound represented by the general formula (N-1-3) is preferably selected from compounds represented by the formulas (N-1-3.1) to (N-1-3.21), More preferably, it is selected from the compounds represented by the formulas (N-1-3.1) to (N-1-3.7) and the formula (N-1-3.21), and the formula (N-1- 3.1), formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6) More preferably, it is selected from the compounds described below.

The compounds represented by the formulas (N-1-3.1) to (N-1-3.4), the formula (N-1-3.6) and the formula (N-1-3.21) are 1 The compounds represented by formula (N-1-3.1) and the compound represented by formula (N-1-3.2) can be used alone or in combination of two or more. A combination with a compound, and a combination of two or three selected from the formula (N-1-3.3), the formula (N-1-3.4) and the formula (N-1-3.6) are preferable.

In the formulas (N-1-3.1) to (N-1-3.4), the formula (N-1-3.6) and the formula (N-1-3.21) contained in the liquid crystal composition, The amounts of the compounds shown, alone or in combination, are preferably as follows. That is, the preferable lower limit values are 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

The compound represented by the general formula (N-1-4) is the following compound.

^{Wherein, R N141} and ^{R N142} are each independently the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).

R ^N141 and ^{R N142} are each independently an alkyl group having 1 to 5 carbon atoms, preferably an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5, methyl group, It is more preferably a propyl group, an ethoxy group or a butoxy group.

The compound represented by the general formula (N-1-4) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-4) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when set high, and when Tni is important, the effect is high when set low. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferable lower limit values are 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass. % And 8% by mass.

Further, the compound represented by the general formula (N-1-4) is preferably selected from compounds represented by the formulas (N-1-4.1) to (N-1-4.24), More preferably, it is selected from compounds represented by formulas (N-1-4.1) to (N-1-4.4), and formulas (N-1-4.1) and (N-1-) It is preferably selected from the compounds represented by 4.2) and the formula (N-1-4.4).

The compounds represented by the formulas (N-1-4.1) to (N-1-4.24) can be used alone or in combination of two or more.

The amount of the compounds represented by the formulas (N-1-4.1) to (N-1-4.24) contained in the liquid crystal composition, alone or in combination, is preferably as follows. That is, the preferable lower limit values are 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass. , 8% by mass.

The compound represented by the general formula (N-1-5) is the following compound.

In the formula, R ^N151 and R ^N152 each independently have the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N151 and R ^N152 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an ethyl group, It is preferably a propyl group or a butyl group.

The compounds represented by the general formula (N-1-5) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-5) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when the value is set low, and the effect is high when the value is emphasized when Tni is important. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferable lower limit values are 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass and 20% by mass. The upper limit of the preferred content is 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass with respect to the total amount of the composition of the present invention. , 15% by mass and 13% by mass.

Further, the compound represented by the general formula (N-1-5) is preferably selected from compounds represented by the formulas (N-1-5.1) to (N-1-5.12), More preferably, it is selected from the compounds represented by formula (N-1-5.1), formula (N-1-5.2) and formula (N-1-5.4).

The compounds represented by the formula (N-1-5.1), the formula (N-1-5.2) and the formula (N-1-5.4) may be used alone or in combination of 2 It is also possible to use more than one type.

A compound represented by formula (N-1-5.1), formula (N-1-5.2) and formula (N-1-5.4) contained in the liquid crystal composition, alone or in combination; The amount is preferably as follows. That is, the preferable lower limit values are 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

The compound represented by the general formula (N-1-10) is the following compound.

In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. preferable.

R ^N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and is an ethoxy group, a propoxy group or a butoxy group. Is more preferable.

The compound represented by the general formula (N-1-10) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-10) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when set high, and when Tni is important, the effect is high when set low. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

Further, the compound represented by the general formula (N-1-10) is preferably selected from compounds represented by the formulas (N-1-10.1) to (N-1-10.14), More preferably, it is selected from the compounds represented by formulas (N-1-10.1) to (N-1-10.5), and formulas (N-1-10.1) and (N-1-) More preferably, it is selected from the compounds represented by 10.2).

The compounds represented by formula (N-1-10.1) and formula (N-1-10.2) can be used each alone or two or more of them can be used in combination.

The amount of the compound represented by the formula (N-1-10.1) and the compound represented by the formula (N-1-10.2) contained in the liquid crystal composition, alone or in combination, is preferably as follows. . That is, the preferable lower limit values are 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

The compound represented by the general formula (N-1-11) is the following compound.

In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. preferable.

R ^N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and is an ethoxy group, a propoxy group or a butoxy group. Is more preferable.

The compound represented by the general formula (N-1-11) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-11) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when the value is set low, and the effect is high when the value is emphasized when Tni is important. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

Further, the compound represented by the general formula (N-1-11) is preferably selected from compounds represented by the formulas (N-1-11.1) to (N-1-11.14), More preferably, it is selected from the compounds represented by formulas (N-1-11.1) to (N-1-11.14), and formula (N-1-11.2 and formula (N-1-11) More preferably, it is selected from the compounds represented by 4).

The compounds represented by the formula (N-1-11.2) and the formula (N-1-11.4) can be used alone or in combination of two or more.

The amounts of the compounds represented by formula (N-1-11.2) and formula (N-1-11.4) contained in the liquid crystal composition, alone or in combination, are preferably as follows. . That is, the preferable lower limit values are 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

The compound represented by the general formula (N-1-12) is the following compound.

In the formula, R ^N1121 and R ^N1122 each independently have the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.

R ^N1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an ethoxy group, a propoxy group or a butoxy group. Is more preferable.

The compound represented by the general formula (N-1-12) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-12) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the effect is high when set high, and when Tni is important, the effect is high when set low. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The compound represented by the general formula (N-1-13) is the following compound.

In the formula, R ^N1131 and R ^N1132 each independently have the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group.

R ^N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an ethoxy group, a propoxy group or a butoxy group. Is more preferable.

The compound represented by the general formula (N-1-13) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-13) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The compound represented by the general formula (N-1-14) is the following compound.

In the formula, R ^N1141 and R ^N1142 each independently have the same meaning as R ^N11 and R ^N12 in formula (N-1).

R ^N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group or a butyl group.

R ^N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an ethoxy group, a propoxy group or a butoxy group. Is more preferable.

The compound represented by the general formula (N-1-14) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-14) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

Further, the compound represented by the general formula (N-1-14) is preferably selected from compounds represented by the formulas (N-1-14. 1) to (N-1-14.5), More preferably, it is selected from the compounds represented by the formulas (N-1-14.1) to (N-1-14.3.), And the formula (N-1-14.2) and the formula (N-1- More preferably, it is selected from the compounds represented by 14.3).

The compound represented by the general formula (N-1-20) is the following compound.

In the formula, R ^N1201 and R ^N1202 each independently represent the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1201 and R ^N1202 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group. preferable.

The compound represented by the general formula (N-1-20) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-20) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The compound represented by the general formula (N-1-21) is the following compound.

In the formula, R ^N1211 and R ^N1212 each independently represent the same meaning as R ^N11 and R ^N12 in the general formula (N-1).

R ^N1211 and R ^N1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group. preferable.

The compound represented by the general formula (N-1-21) can be used alone or in combination of two or more kinds.

The amount of the compound represented by the general formula (N-1-21) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The compound represented by the general formula (N-1-22) is the following compound.

In the formula, R ^N1221 and R ^N1222 each independently have the same meaning as R ^N11 and R ^N12 in formula (N-1).

R ^N1221 and R ^N1222 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more preferably an ethyl group, a propyl group or a butyl group. preferable.

The compound represented by the general formula (N-1-22) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (N-1-22) contained in the liquid crystal composition is preferably set higher when the improvement of Δε is important, and the solubility at low temperature is important. In this case, the higher the effect is, the higher the effect is. If the Tni is important, the higher the effect is. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass and 20% by mass. On the other hand, the preferable upper limit values are 35% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 5% by mass. %.

Further, the compound represented by the general formula (N-1-22) is preferably selected from compounds represented by the formulas (N-1-22. 1) to (N-1-22. 12), More preferably, it is selected from the compounds represented by formulas (N-1-22.1) to (N-1-22.5), and formulas (N-1-22.1) to (N-1-22) More preferably, it is selected from the compounds represented by 4).

The liquid crystal composition may further contain at least one selected from compounds (liquid crystal molecules) represented by the following general formula (L). The compound represented by the general formula (L) has no or extremely low dielectric anisotropy. Therefore, various characteristics of the liquid crystal composition can be adjusted by incorporating such a compound into the liquid crystal composition.

In the formula, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, but any one or two or more non-adjacent —CH ₂ — groups present in the alkyl group are represented. May each independently be substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—.

n ^L1 represents 0, 1, 2 or 3.

A ^L1 , A ^L2 and A ^L3 are each independently
(A) 1,4-cyclohexylene group (any one or two or more non-adjacent —CH ₂ — present in the group may be substituted with —O—),
(B) 1,4-phenylene group (any one or two or more non-adjacent -CH = present in the group may be substituted with -N =), and (c) naphthalene- 2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (any one present in the group or non-adjacent 2 More than one -CH = may be replaced by -N =.)
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom.

Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —. It represents OCF ₂ —, —CF ₂ O—, —CH═NN═CH—, —CH═CH—, —CF═CF— or —C≡C—.

When n ^L1 is 2 or 3 and a plurality of A ^L2 are present, they may be the same or different.

When n ^L1 is 2 or 3 and a plurality of Z ^L3 are present, they may be the same or different.

However, compounds represented by the general formulas (N-1), (N-2) and (N-3) are excluded.

The compound represented by the general formula (L) can be used alone or in combination of two or more.

The type of compound that can be used in combination is not particularly limited, but is appropriately selected according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence.

The type of compound used is, for example, one type in one embodiment of the present invention. Alternatively, the types of compounds used in another embodiment of the present invention are two types, three types, four types, five types, six types, seven types, and eight types. And 9 types, and 10 or more types.

The amount of the compound represented by the general formula (L) contained in the liquid crystal composition depends on the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, the process compatibility, the dripping mark, the burn-in, the dielectric property. It is appropriately adjusted according to the required performance such as rate anisotropy.

The preferred lower limit is 1% by mass, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass. On the other hand, the preferable upper limit values are 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass and 25% by mass.

When it is necessary to keep the viscosity of the liquid crystal composition low and increase the response speed, it is preferable that the lower limit value and the upper limit value are high. Further, when it is necessary to keep the Tni of the liquid crystal composition high and to improve the temperature stability, it is preferable that the lower limit value and the upper limit value are high. Further, when it is desired to increase the dielectric anisotropy of the liquid crystal composition in order to keep it low, the lower limit and the upper limit are preferably low.

When reliability is important, both R ^L1 and R ^L2 are preferably alkyl groups, and when importance is attached to reducing volatility, both R ^L1 and R ^L2 are alkoxy groups. It is preferable that when importance is attached to the reduction of the viscosity of the liquid crystal composition, at least one of R ^L1 and R ^L2 is an alkenyl group.

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, more preferably 0 or 1, and when importance is attached to compatibility with other liquid crystal molecules, It is more preferable that the number is one.

When R ^L1 and R ^L2 are bonded to a ring structure which is a benzene ring (aromatic ring), R ¹ and R ^L2 are linear alkyl groups having 1 to 5 carbon atoms, and linear alkyl groups having 1 to 5 carbon atoms. It is preferably an alkoxy group having 4 or an alkenyl group having 4 to 5 carbon atoms, and when they are bonded to a saturated ring structure such as a cyclohexane ring, a pyran ring or a dioxane ring, a linear carbon atom It is preferably an alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the number of carbon atoms (when oxygen atoms are included, the total number of carbon atoms and the number of oxygen atoms) is preferably 5 or less, and linear Is also preferable.

The black dots in each formula represent carbon atoms in the ring structure.

n ^L1 is preferably 0 when the response speed is important, is preferably 2 or 3 in order to improve the maximum temperature of the nematic phase, and is 1 in order to balance these. It is preferable. Further, in order to satisfy the properties required for the liquid crystal composition, it is preferable to use a plurality of types of compounds represented by the general formula (L) having different values of n ^L1 in combination.

A ^L1 , A ^L2, and A ^L3 are each independently preferably aromatic when it is required to increase Δn, and preferably aliphatic for improving the response speed. .

Specifically, A ^L1 , A ^L2 and A ^L3 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, 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 is preferable, and More preferably, it is any of the groups of Chemical formula 39, and even more preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^L1 and Z ^L2 are preferably a single bond when the response speed is important.

The compound represented by the general formula (L) preferably has 0 or 1 halogen atom present in the molecule.

More specifically, the compound represented by the general formula (L) is preferably selected from the compounds represented by the following general formulas (L-1) to (L-7).

化合物 The compound represented by formula (L-1) is the following compound.

In the formula, R ^L11 and R ^L12 each independently have the same meaning as R ^L1 and R ^L2 in formula (L).

R ^L11 and R ^L12 are each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear chain having 2 to 5 carbon atoms. Is preferably an alkenyl group.

The compound represented by the general formula (L-1) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (L-1) contained in the liquid crystal composition is set as follows. That is, the preferable lower limit value is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 15% by mass, 20% by mass, 25% by mass, 30% by mass, 35% by mass. %, 40 mass%, 45 mass%, 50 mass%, 55 mass%. On the other hand, the preferable upper limit values are 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass. %, 40% by mass, 35% by mass, 30% by mass, and 25% by mass.

When it is necessary to keep the viscosity of the liquid crystal composition low and increase the response speed, it is preferable that the lower limit value and the upper limit value are high. Further, when it is necessary to keep the Tni of the liquid crystal composition high and enhance the temperature stability, it is preferable that the lower limit value is moderate and the upper limit value is moderate. Further, when it is desired to increase the dielectric anisotropy of the liquid crystal composition in order to keep it low, the lower limit and the upper limit are preferably low.

The compound represented by the general formula (L-1) is preferably selected from the compounds represented by the general formula (L-1-1).

In the formula, R ^L12 has the same meaning as R ^L12 in formula (L-1).

The compound represented by formula (L-1-1) is preferably selected from compounds represented by formulas (L-1-1.1) to (L-1-1.3), L-1-1.2) and a compound represented by the formula (L-1-1.3) are more preferred, and a compound represented by the formula (L-1-1.3) Is more preferable.

The amount of the compound represented by the formula (L-1-1.3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass and 3% by mass.

The compound represented by the general formula (L-1) is preferably selected from the compounds represented by the general formula (L-1-2).

In the formula, R ^L12 has the same meaning as R ^L12 in formula (L-1).

量 The amount of the compound represented by formula (L-1-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass%. %. On the other hand, the preferable upper limit value is 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%.

Further, the compound represented by the general formula (L-1-2) is preferably selected from compounds represented by the formulas (L-1-2.1) to (L-1-2.4), More preferably, it is selected from the compounds represented by formulas (L-1-2.2) to (L-1-2.4).

Particularly, the compound represented by the formula (L-1-2.2) is preferable because it particularly improves the response speed of the liquid crystal composition. Further, when obtaining Tni higher than the response speed, it is preferable to use the compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The total amount of the compound represented by formula (L-1-2.3) and the compound represented by formula (L-1-2.4) contained in the liquid crystal composition is the solubility at low temperature. In order to improve the content, it is not preferable to set it to 30% by mass or more.

The amount of the compound represented by formula (L-1-2.2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 10 mass%, 15 mass%, 18 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 33 mass%, 35 mass%, 38 mass%. % And 40% by mass. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 43% by mass, 40% by mass, 38% by mass, 35% by mass, 32% by mass, 30% by mass, 27% by mass. %, 25% by mass, and 22% by mass.

The total amount of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) contained in the liquid crystal composition is as follows. Is preferred. That is, the preferable lower limit values are 10% by mass, 15% by mass, 20% by mass, 25% by mass, 27% by mass, 30% by mass, 35% by mass, and 40% by mass. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 43% by mass, 40% by mass, 38% by mass, 35% by mass, 32% by mass, 30% by mass, 27% by mass. %, 25% by mass, and 22% by mass.

The compound represented by the general formula (L-1) is preferably selected from the compounds represented by the general formula (L-1-3).

In the formula, R ^L13 and R ^L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

R ^L13 and R ^L14 are each independently a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear chain having 2 to 5 carbon atoms. Is preferably an alkenyl group.

The amount of the compound represented by formula (L-1-3) contained in the liquid crystal composition is preferably as follows. That is, the lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass and 30% by mass. On the other hand, the preferable upper limit is 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 37% by mass, 35% by mass, 33% by mass, 30% by mass, 27% by mass, 25% by mass. %, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.

Further, the compound represented by the general formula (L-1-3) is preferably selected from compounds represented by the formulas (L-1-3.1) to (L-1-3.13), More preferably, it is selected from the compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4).

Particularly, the compound represented by the formula (L-1-3.1) is preferable because it particularly improves the response speed of the liquid crystal composition. Further, when obtaining Tni higher than the response speed, the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11), or the formula (L- It is preferable to use the compound represented by 1-3.12). Note that a compound represented by the formula (L-1-3.3), a compound represented by the formula (L-1-3.4), and a compound represented by the formula (L-1-3) contained in the liquid crystal composition. 0.11) and the compound represented by the formula (L-1-3.13), the total amount is preferably 20% by mass or more in order to improve the solubility at low temperature. Absent.

The amount of the compound represented by formula (L-1-3.1) contained in the liquid crystal composition is preferably as follows. That is, the preferred lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass and 20% by mass. On the other hand, the preferable upper limit values are 20% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass and 6% by mass.

The compound represented by the general formula (L-1) is preferably selected from the compounds represented by the general formula (L-1-4) and / or (L-1-5).

In the formula, R ^L15 and R ^L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

R ^L15 and R ^L16 each independently represent a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or a linear chain having 2 to 5 carbon atoms. Is preferably an alkenyl group.

The amount of the compound represented by the formula (L-1-4) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 25% by mass, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass and 10% by mass.

The amount of the compound represented by formula (L-1-5) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 25% by mass, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass and 10% by mass.

Further, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-5.3). The compound is preferably selected from the compounds, and more preferably selected from the compounds represented by the formula (L-1-4.2) and the formula (L-1-5.2).

The amount of the compound represented by the formula (L-1-4.2) contained in the liquid crystal composition is preferably as follows. That is, the preferred lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass and 20% by mass. On the other hand, the preferable upper limit values are 20% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass and 6% by mass.

Formula (L-1-1.3), Formula (L-1-2.2), Formula (L-1-3.1), Formula (L-1-3.3), Formula (L-1- 3.4), two or more compounds selected from the compounds represented by the formula (L-1-3.11) and the formula (L-1-3.12), or the compound represented by the formula (L-1-1) .3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and formula (L-1-3.4). It is also preferable to use two or more kinds selected from the compounds represented by L-1-4.2) in combination.

The total amount of these compounds contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, and 23% by mass. %, 25% by mass, 27% by mass, 30% by mass, 33% by mass, and 35% by mass. On the other hand, the preferable upper limit values are 80% by mass, 70% by mass, 60% by mass, 50% by mass, 45% by mass, 40% by mass, 37% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass. %, 25% by mass, 23% by mass, and 20% by mass.

When importance is placed on the reliability of the liquid crystal composition, the compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4) It is preferable to use two or more kinds selected from the following in combination, and when importance is attached to the response speed of the liquid crystal composition, they are represented by the formula (L-1-1.3) and the formula (L-1-2.2). It is preferable to use two or more compounds selected from the following compounds in combination.

The compound represented by the general formula (L-1) is preferably selected from the compounds represented by the general formula (L-1-6).

In the formula, R ^L17 and R ^L18 each independently represent a methyl group or a hydrogen atom.

The amount of the compound represented by formula (L-1-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1 mass%, 5 mass%, 10 mass%, 15 mass%, 17 mass%, 20 mass%, 23 mass%, 25 mass%, 27 mass%, 30 mass%, 35 mass%. %. On the other hand, the preferable upper limit value is 60 mass%, 55 mass%, 50 mass%, 45 mass%, 42 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 30 mass%.

Further, the compound represented by the general formula (L-1-6) is preferably selected from the compounds represented by the formulas (L-1-6.1) to (L-1-6.3).

The compound represented by the general formula (L-2) is the following compound.

In the formula, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).

R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

R ^L22 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-2) can be used alone or in combination of two or more kinds.

The amount of the compound represented by the general formula (L-2) contained in the liquid crystal composition is high when the solubility at low temperature is important, and the effect is high, on the contrary, the response speed is important. In this case, setting it lower will be more effective. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the range of the amount to the middle.

The preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass and 3% by mass.

Further, the compound represented by the general formula (L-2) is preferably selected from compounds represented by the formulas (L-2.1) to (L-2.6), and the compound represented by the formula (L-2. More preferably, it is selected from the compounds represented by 1), formula (L-2.3), formula (L-2.4) and formula (L-2.6).

化合物 The compound represented by formula (L-3) is the following compound.

In the formula, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).

R ^L31 and R ^L32 are preferably each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-3) can be used alone or in combination of two or more.

The amount of the compound represented by formula (L-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass and 3% by mass.

The amount of the compound represented by the general formula (L-3) contained in the liquid crystal composition is set high to obtain a high birefringence, and on the contrary, when high Tni is important. Is effective when set to a low value. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the range of the amount to the middle.

Further, the compound represented by the general formula (L-3) is preferably selected from compounds represented by the formulas (L-3.1) to (L-3.7), and the compound represented by the formula (L-3. More preferably, it is selected from the compounds represented by 2) to (L-3.5).

化合物 The compound represented by formula (L-4) is as follows.

In the formula, R ^L41 and R ^L42 each independently have the same meaning as R ^L1 and R ^L2 in the general formula (L).

R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

R ^L42 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-4) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (L-4) contained in the liquid crystal composition depends on the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, the process compatibility, the dripping mark, and the burn-in. , The dielectric anisotropy and the like are appropriately adjusted according to the required performance.

The preferred lower limit is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, 26% by mass, 30% by mass, 35% by mass and 40% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass and 5% by mass.

Further, the compound represented by the general formula (L-4) is preferably selected from the compounds represented by the formulas (L-4.1) to (L-4.3).

The liquid crystal composition may contain a compound represented by the formula (L-4.1) depending on required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The compound represented by the formula (L-4.2) may be contained, or the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) It may contain both the compound and the compounds represented by the formulas (L-4.1) to (L-4.3).

The amount of the compound represented by formula (L-4.1) or formula (L-4.2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 3% by mass, 5% by mass, 7% by mass, 9% by mass, 11% by mass, 12% by mass, 13% by mass, 18% by mass, and 21% by mass. On the other hand, the preferable upper limit values are 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass. % And 8% by mass.

When the liquid crystal composition contains both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2), it is included in the liquid crystal composition. The total amount is preferably as follows. That is, the preferable lower limit values are 15% by mass, 19% by mass, 24% by mass, and 30% by mass. On the other hand, the preferable upper limit values are 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

The compound represented by the general formula (L-4) is preferably selected from the compounds represented by the formulas (L-4.4) to (L-4.6), and the compound represented by the formula (L-4. More preferably, it is the compound represented by 4).

The liquid crystal composition may contain a compound represented by the formula (L-4.4) depending on required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. Of course, the compound represented by the formula (L-4.5) may be contained, and the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) Both may be contained.

The amount of the compound represented by formula (L-4.4) or formula (L-4.5) in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 3% by mass, 5% by mass, 7% by mass, 9% by mass, 11% by mass, 12% by mass, 13% by mass, 18% by mass, and 21% by mass. On the other hand, the preferable upper limit values are 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass. % And 8% by mass.

When the liquid crystal composition contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5), it is included in these liquid crystal compositions. The total amount is preferably as follows. That is, the preferable lower limit values are 15% by mass, 19% by mass, 24% by mass, and 30% by mass. On the other hand, the preferable upper limit values are 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass and 13% by mass.

Further, the compound represented by the general formula (L-4) is preferably selected from compounds represented by the formulas (L-4.7) to (L-4.10), and particularly, the compound represented by the formula (L- It is preferably a compound represented by 4.9).

化合物 The compound represented by formula (L-5) is as follows.

In the formula, R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).

R ^L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

R ^L52 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-5) can be used alone or in combination of two or more.

The amount of the compound represented by the general formula (L-5) contained in the liquid crystal composition depends on the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, the process compatibility, the dripping mark, and the burn-in. , The dielectric anisotropy and the like are appropriately adjusted according to the required performance.

Further, the compound represented by the general formula (L-5) is preferably the compound represented by the formula (L-5.1) or the formula (L-5.2), and particularly, the compound represented by the formula (L- It is preferably a compound represented by 5.1).

The amount of each compound contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, and 7% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, and 9% by mass.

The compound represented by the general formula (L-5) is preferably the compound represented by the formula (L-5.3) or the formula (L-5.4).

Further, the compound represented by the general formula (L-5) is preferably selected from the compounds represented by the formulas (L-5.5) to (L-5.7), and particularly, the compound represented by the formula (L- It is preferably a compound represented by 5.7).

The compound represented by the general formula (L-6) is the following compound.

In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).

X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom.

R ^L61 and R ^L62 are preferably each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

It is preferable that one of X ^L61 and X ^L62 is a fluorine atom and the other is a hydrogen atom.

The compound represented by the general formula (L-6) can be used alone or in combination of two or more.

量 The amount of the compound represented by formula (L-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, 26% by mass. %, 30% by mass, 35% by mass, and 40% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass and 5% by mass. The amount of the compound represented by the general formula (L-6) is preferably increased when emphasis is placed on increasing Δn, and is smaller when emphasis is placed on precipitation at low temperature. preferable.

Furthermore, the compound represented by the general formula (L-6) is preferably selected from the compounds represented by the formulas (L-6.1) to (L-6.9).

The type of compound that can be used in combination is not particularly limited, but it is preferable to select 1 to 3 types from the compounds represented by the formulas (L-6.1) to (L-6.9), and preferably 1 to 4 It is more preferable to select the type.

In addition, since the compound to be used in combination has a wide molecular weight distribution, which is effective for solubility, for example, one of the compounds represented by the formula (L-6.1) and the formula (L-6.2) is selected. , One of the compounds represented by formula (L-6.4) and formula (L-6.5), and one represented by formula (L-6.6) and formula (L-6.7) It is preferable to select one kind from the compounds represented by the formula (L-6.8) and the compound represented by the formula (L-6.9) and to combine them appropriately.

Among them, represented by formula (L-6.1), formula (L-6.3), formula (L-6.4), formula (L-6.6) and formula (L-6.9). It is preferable to include a compound.

Further, the compound represented by the general formula (L-6) is preferably selected from compounds represented by the formulas (L-6.10) to (L-6.17), and the compound represented by the formula (L-6. The compound represented by 11) is more preferable.

The amount of each compound contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, and 7% by mass. On the other hand, the upper limit of the preferable content is 20 mass%, 15 mass%, 13 mass%, 10 mass%, 9 mass%.

化合物 The compound represented by formula (L-7) is the following compound.

In the formula, R ^L71 and R ^L72 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).

A ^L71 and A ^L72 each independently represent the same meaning as A ^L2 and A ^L3 in formula (L), but the hydrogen atoms present in A ^L71 and A ^L72 are each independently a fluorine atom. May be replaced with.

Z ^L71 has the same meaning as Z ^L2 in formula (L).

X ^L71 and X ^L72 each independently represent a fluorine atom or a hydrogen atom.

In the formula, R ^L71 and R ^L72 are preferably each independently 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.

A ^L71 and A ^L72 are preferably each independently a 1,4-cyclohexylene group or a 1,4-phenylene group. The hydrogen atoms present in A ^L71 and A ^L7 may be each independently substituted with a fluorine atom.

Z ^L71 is preferably a single bond or COO—, and more preferably a single bond.

X ^L71 and X ^L72 are preferably hydrogen atoms.

The types of compounds used are, for example, one type, two types, three types, and four types in one embodiment of the present invention.

The amount of the compound represented by the general formula (L-7) contained in the liquid crystal composition depends on the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, the process compatibility, the dripping mark, and the burn-in. , The dielectric anisotropy and the like are appropriately adjusted according to the required performance.

好ましい The preferable lower limit is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 10% by mass and 5% by mass.

The amount of the compound represented by the general formula (L-7) is preferably large when a liquid crystal composition having a high Tni is required and is small when a liquid crystal composition having a low viscosity is required. Is preferred.

Further, the compound represented by the general formula (L-7) is preferably selected from compounds represented by the formulas (L-7.1) to (L-7.4), and the compound represented by the formula (L-7. More preferably, it is the compound represented by 2).

Further, the compound represented by the general formula (L-7) is preferably selected from the compounds represented by the formulas (L-7.11) to (L-7.13), and the compound represented by the formula (L-7. It is preferably a compound represented by 11).

Further, the compound represented by the general formula (L-7) is preferably selected from compounds represented by the formulas (L-7.21) to (L-7.23), and the compound represented by the formula (L-7. The compound represented by 21) is more preferable.

Further, the compound represented by the general formula (L-7) is preferably selected from compounds represented by the formulas (L-7.31) to (L-7.34), and the compound represented by the formula (L-7. 31) and / or a compound represented by the formula (L-7.32) are more preferable.

Further, the compound represented by the general formula (L-7) is preferably selected from the compounds represented by the formulas (L-7.41) to (L-7.44), and the compound represented by the formula (L-7. 41) and / or the compound represented by the formula (L-7.42) is more preferable.

Also, the compound represented by the general formula (L-7) is preferably selected from the compounds represented by the formulas (L-7.51) to (L-7.53).

The liquid crystal composition as described above preferably does not contain a compound having a structure in which oxygen atoms are bonded to each other such as a peracid (—CO—OO—) structure in the molecule.

When the reliability and long-term stability of the liquid crystal composition are emphasized, the amount of the compound having a carbonyl group contained in the liquid crystal composition is preferably 5% by mass or less, and 3% by mass or less. Is more preferable, it is more preferable to be 1 mass% or less, and it is most preferable to be substantially 0 (zero) mass%.

When importance is attached to stability by UV irradiation, the amount of the compound substituted with chlorine atom in the liquid crystal composition is preferably 15% by mass or less, more preferably 10% by mass or less, It is more preferably 8% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably substantially 0 (zero)% by mass.

Further, it is preferable to increase the amount of the compound having a 6-membered ring structure in the molecule contained in the liquid crystal composition, specifically, 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 95 mass% or more, and most preferably substantially 100 mass%.

In order to prevent or suppress the deterioration of the liquid crystal composition due to oxidation, it is preferable to reduce the amount of the compound having a cyclohexene ring as a ring structure contained in the liquid crystal composition, specifically, 10% by mass or less. It is preferably 8% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and substantially 0 (zero)% by mass. Most preferred.

Further, in order to prevent or suppress the deterioration of the liquid crystal composition due to oxidation, it is preferable to reduce the amount of the compound having —CH═CH— as a linking group contained in the liquid crystal composition. It is preferably not more than 5% by mass, more preferably not more than 5% by mass, and further preferably substantially 0 (zero)% by mass.

When it is important to improve the viscosity (η) of the liquid crystal composition and the nematic phase-isotropic liquid phase transition temperature (Tni), a hydrogen atom may be replaced by a halogen atom. It is preferable to reduce the amount of the compound having a methylbenzene-1,4-diyl group in the molecule contained in the liquid crystal composition. Specifically, it is preferably 10% by mass or less, and 5% by mass or less. Is more preferable, and it is further preferable that the content is substantially 0 (zero) mass%.

When the compound (liquid crystal molecule or the like) contained in the liquid crystal composition has a cyclohexylene group having an alkenyl group bonded as a side chain, the alkenyl group preferably has 2 to 5 carbon atoms. When the compound contained in the liquid crystal composition has a phenylene group to which an alkenyl group is bonded as a side chain, the alkenyl group preferably has 4 to 5 carbon atoms, and the alkenyl group does not have a carbon atom. It is preferable that the saturated bond and the phenylene group are not directly bonded.

Further, when importance is attached to the stability of the liquid crystal composition, the amount of the compound having an alkenyl group as a side chain and having a 2,3-difluorobenzene-1,4-diyl group in the liquid crystal composition Is preferably less than 10% by mass, more preferably not more than 5% by mass, even more preferably substantially 0 (zero)% by mass.

The average elastic constant (K _AVG ) of the liquid crystal composition is preferably 10 to 25. However, the preferable lower limit value is 10, 10.5, 11, 11.5, 12, 12.3, 12.5, 12.8, 13, 13.3, 13.5, 13.8, 14, 14.3, 14.5, 14.8, 15, 15.3, 15.5, 15.8, 16, 16.3, 16.5, 16.8, 17, 17.3, 17.5, 17.8 and 18. On the other hand, the preferable upper limit values are 25, 24.5, 24, 23.5, 23, 22.8, 22.5, 22.3, 22, 21.8, 21.5, 21.3, 21, 20.8, 20.5, 20.3, 20, 19.8, 19.5, 19.3, 19, 18.8, 18.5, 18.3, 18, 17.8, 17.5, 17.3 and 17.

When importance is attached to reduction of power consumption, it is effective to suppress the light amount of the backlight, and therefore it is preferable to improve the light transmittance of the liquid crystal display element 1. Therefore, it is preferable to set the value of K _AVG low. When emphasis is placed on improving the response speed, it is preferable to set a high value of K _AVG .

The value of the refractive index anisotropy (Δn) (hereinafter, simply referred to as “refractive index anisotropy”) at 25 ° C. of the liquid crystal composition is preferably about 0.08 to 0.13, and a value of 0. It is more preferably about 09 to 0.12.

The rotational viscosity (γ1) of the liquid crystal composition at 25 ° C. (hereinafter, also simply referred to as “rotational viscosity”) is preferably less than 165 mPa · s, more preferably about 80 to 145 mPa · s, and more preferably about 90 to 130 mPa · s. More preferable. By using the liquid crystal composition having such a rotational viscosity, it is possible to prevent the response speed of the liquid crystal layer 4 (liquid crystal display element 1) from decreasing.

Further, in the liquid crystal composition, it is preferable that Z, which is a function of the rotational viscosity and the value of refractive index anisotropy, shows a specific value.

In the formula, γ1 represents rotational viscosity and Δn represents refractive index anisotropy.

Z is preferably 13,000 mPa · s or less, more preferably 12,000 mPa · s or less, and further preferably 11,000 mPa · s or less.

The nematic phase-isotropic liquid phase transition temperature (Tni) of the liquid crystal composition is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, and further preferably 80 ° C. or higher. By using the liquid crystal composition having such Tni, it is possible to obtain the liquid crystal layer 4 (liquid crystal display element 1) which can be stably driven in the temperature range in which it is actually used.

The specific resistance of the liquid crystal composition is preferably 10 ¹² Ω · m or more, more preferably 10 ¹³ Ω · m or more, and further preferably 10 ¹⁴ Ω · m or more.

The absolute value of the dielectric anisotropy (Δε) at 25 ° C. of the liquid crystal composition is preferably about 2.5 to 5, more preferably about 2.6 to 4.5, and 2.7. It is more preferably about 4 to about 4, more preferably about 2.8 to 3.5. By using the liquid crystal composition having such a dielectric anisotropy, the liquid crystal layer 4 (liquid crystal display element 1) can be driven at a lower voltage.

The liquid crystal composition described above is, in addition to the above liquid crystal molecules, other compounds (molecules) such as ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, and ultraviolet absorbers depending on the application. May be included.

However, when the chemical stability of the liquid crystal composition is required, it is preferable that the other compound does not have a chlorine atom in its structure. Further, when stability of the liquid crystal composition against light such as ultraviolet rays is required, other compounds include a condensed ring having a long conjugation length represented by a naphthalene ring or the like in its structure and an absorption peak in the ultraviolet region. It is preferable not to have.

(Liquid crystal display device)
Next, a liquid crystal display device including a liquid crystal layer formed of the above liquid crystal composition will be described.

FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display device, and FIG. 2 is an enlarged plan view of a region surrounded by I line in FIG.

Note that, for convenience, in FIG. 1 and FIG. 2, the dimensions and ratios of the respective parts are exaggerated and may be different from the actual ones. Further, the materials, dimensions, and the like shown below are examples, and the present invention is not limited to them, and can be appropriately changed within the scope of the invention.

The liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF arranged to face each other, and a liquid crystal layer 4 sandwiched between the active matrix substrate AM and the color filter substrate CF. ing.

The active matrix substrate AM includes the first substrate 2, the pixel electrode layer 5 provided on the surface of the first substrate 2 on the liquid crystal layer 4 side, and the surface of the first substrate 2 on the opposite side of the liquid crystal layer 4. It has the 1st polarizing plate 7 provided.

On the other hand, the color filter substrate CF is formed on the second substrate 3, the common electrode layer 6 provided on the liquid crystal layer 4 side of the second substrate 3, and the surface of the second substrate 3 opposite to the liquid crystal layer 4. It has a second polarizing plate 8 provided and a color filter 9 provided between the second substrate 3 and the common electrode layer 6.

That is, the liquid crystal display element 1 according to the present embodiment includes the first polarizing plate 7, the first substrate 2, the pixel electrode layer 5, the liquid crystal layer 4, the common electrode layer 6, and the color filter 9. The second substrate 3 and the second polarizing plate 8 are laminated in this order.

The first substrate 2 and the second substrate 3 are each formed of a material having flexibility such as a glass material or a plastic material.

Both the first substrate 2 and the second substrate 3 may have a light-transmitting property, or only one of them may have a light-transmitting property. In the latter case, the other substrate may be composed of an opaque material such as a metallic material or a silicon material.

As shown in FIG. 2, the pixel electrode layer 5 includes a plurality of gate bus lines 11 for supplying a scanning signal, a plurality of data bus lines 12 for supplying a display signal, and a plurality of pixel electrodes 13. Have It should be noted that FIG. 2 shows a pair of

gate bus lines

11 and 11 and a pair of

data bus lines

12 and 12.

The plurality of gate bus lines 11 and the plurality of data bus lines 12 are arranged in a matrix so as to intersect with each other, and the unit pixel of the liquid crystal display element 1 is formed by the region surrounded by these. One pixel electrode 13 is formed in each unit pixel.

The pixel electrode 13 has a structure (so-called fishbone structure) including two trunk portions that are orthogonal to each other and have a cross shape, and a plurality of branch portions that branch from each trunk portion and extend outward. There is.

A Cs electrode 14 is provided between the pair of

gate bus lines

11, 11 substantially parallel to the gate bus line 11. Further, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided in the vicinity of an intersection where the gate bus line 11 and the data bus line 12 intersect each other. A contact hole 17 is provided in the drain electrode 16.

The gate bus line 11 and the data bus line 12 are preferably formed of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or an alloy containing these, and Mo, Al or It is more preferable to form an alloy containing these.

The pixel electrode 13 is composed of, for example, a transparent electrode in order to improve the light transmittance. The transparent electrode is formed by sputtering a compound such as ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, and AZTO (AlZnSnO).

The average thickness of the transparent electrode is preferably about 10 to 200 nm. Further, in order to reduce the electric resistance, a transparent electrode can be formed as a polycrystalline ITO film by baking an amorphous ITO film.

On the other hand, the common electrode layer 6 has, for example, a plurality of striped common electrodes (transparent electrodes) that are provided side by side. This common electrode can also be formed similarly to the pixel electrode 13.

The color filter 9 can be formed by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like.

In the pigment dispersion method, a curable coloring composition for a color filter is supplied on the second substrate 3 in a predetermined pattern, and then cured by heating or light irradiation. The color filter 9 can be obtained by performing this operation for three colors of red, green, and blue.

Note that the color filter 9 may be arranged on the first substrate 2 side.

Further, the liquid crystal display element 1 may be provided with a black matrix (not shown) from the viewpoint of preventing light leakage. This black matrix is preferably formed in a portion corresponding to the thin film transistor.

The black matrix may be arranged on the second substrate 3 side together with the color filter 9, or may be arranged on the first substrate 2 side together with the color filter 9, and the black matrix may be arranged on the first substrate 2 side. The color filters 9 may be individually arranged on the second substrate 3 side. Further, the black matrix may be formed by a portion in which the respective colors of the color filter 9 are overlapped and the transmittance is reduced.

The active matrix substrate AM and the color filter substrate CF are attached to each other in their peripheral regions by a sealing material (sealing material) composed of an epoxy thermosetting composition or the like.

Note that a spacer may be arranged between the active matrix substrate AM and the color filter substrate CF so as to maintain a distance therebetween. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, resin spacer columns formed by a photolithography method, and the like.

The average distance between the active matrix substrate AM and the color filter substrate CF (that is, the average thickness of the liquid crystal layer 4) is preferably about 1 to 100 μm.

The first polarizing plate 7 and the second polarizing plate 8 can be designed to have a good viewing angle and good contrast by adjusting the positional relationship of their transmission axes. Specifically, the first polarizing plate 7 and the second polarizing plate 8 are preferably arranged so that their transmission axes are orthogonal to each other so as to operate in the normally black mode. In particular, it is preferable that one of the first polarizing plate 7 and the second polarizing plate 8 is arranged such that the transmission axis thereof is parallel to the alignment direction of the liquid crystal molecules when no voltage is applied.

When the first polarizing plate 7 and the second polarizing plate 8 are used, the product of the refractive index anisotropy (Δn) of the liquid crystal layer 4 and the average thickness of the liquid crystal layer 4 so that the contrast becomes maximum. Is preferably adjusted. Furthermore, the liquid crystal display element 1 may include a retardation film for widening the viewing angle.

In the liquid crystal display element 1, an alignment film such as a polyimide alignment film is provided on the liquid crystal layer 4 side of at least one of the active matrix substrate AM and the color filter substrate CF so as to be in contact with the liquid crystal layer 4. it can.

(Method of manufacturing liquid crystal display element)
Next, a method of manufacturing such a liquid crystal display element 1 will be described.

The method for manufacturing a liquid crystal display element of the present embodiment is performed by a preparation step [1] for preparing a substrate and a liquid crystal composition, an assembly step [2] for assembling the liquid crystal display element 1, and a polymerization for polymerizing the polymerizable monomers A and B. It has a process [3] and a curing process [4] for curing the sealing material.

[1] Preparation Step First, the active matrix substrate AM, the color filter substrate CF, and the liquid crystal composition as described above are prepared.

[2] Assembly Step Next, the seal material is drawn in a closed-loop bank shape using a dispenser along at least one edge of the active matrix substrate AM and the color filter substrate CF.

After that, after dropping a predetermined amount of the liquid crystal composition inside the sealing material, the active matrix substrate AM and the color filter substrate CF are arranged to face each other so as to contact the liquid crystal composition under reduced pressure.

In such a drop injection (ODF: One Drop Fill) method, it is necessary to add an optimum injection amount according to the size of the liquid crystal display element 1. The liquid crystal composition as described above has little influence on, for example, a sudden change in pressure or impact in a dropping device generated at the time of dropping, and can be stably dropped for a long time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

Especially, small liquid crystal display elements frequently used in smartphones have a small optimal injection amount of the liquid crystal composition, and thus it is difficult to control the deviation amount within a certain range. However, by using the liquid crystal composition as described above, a stable and optimum injection amount can be accurately dropped even in a small liquid crystal display element.

Further, according to the ODF method, it is possible to suppress the generation of drop marks when the liquid crystal composition is dropped on the substrate. It should be noted that the drop mark is a phenomenon in which the mark on which the liquid crystal composition is dropped appears white when black is displayed.

[3] Polymerization Step Next, the polymerizable monomers A and B are polymerized by irradiating the liquid crystal composition with active energy rays such as ultraviolet rays and electron rays.

Thereby, a polymer layer for controlling the liquid crystal alignment is formed at the interface of the liquid crystal layer 4, and the liquid crystal display element 1 is obtained.

▽ In order to give a sufficient pretilt angle to liquid crystal molecules, an appropriate polymerization rate is desirable. Therefore, during the polymerization, it is preferable to irradiate the active energy rays singly, in combination, or sequentially. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used.

When the polymerization is performed in a state where the two substrates face each other so as to be in contact with the liquid crystal composition as in the present embodiment, at least the substrate located on the irradiation surface side is appropriate for the active energy ray. It is necessary to have high permeability.

Also, polymerization may be carried out in multiple stages as follows. Specifically, first, conditions such as an electric field, a magnetic field, or temperature are adjusted to change the alignment state of liquid crystal molecules. In this state, the active energy ray is irradiated to the liquid crystal composition to polymerize the polymerizable monomer A and the polymerizable monomer B. Next, the liquid crystal composition is irradiated with an activation energy ray without applying an electric field or a magnetic field to polymerize the remaining polymerizable monomers A and B.

In particular, when using ultraviolet rays, it is preferable to irradiate the ultraviolet rays while applying an alternating electric field to the liquid crystal composition.

The frequency of the applied alternating current is preferably about 10 Hz to 10 kHz, more preferably about 60 Hz to 10 kHz.

The AC voltage to be applied is selected depending on the desired pretilt angle of the liquid crystal display element 1. That is, the pretilt angle of the liquid crystal display element 1 can be controlled by adjusting the applied alternating voltage.

The temperature when irradiating with ultraviolet rays is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. The specific temperature is preferably close to room temperature, that is, typically about 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, a fluorescent tube, etc. can be used.

Further, the ultraviolet ray to be irradiated is preferably an ultraviolet ray having a wavelength not in the absorption wavelength range of the liquid crystal composition, and it is more preferable to use by cutting a predetermined wavelength if necessary.

The intensity of the ultraviolet rays to be applied is preferably about 0.1 mW / cm ² to 100 W / cm ² , and more preferably about ² mW / cm ² to 50 W / cm ² . In addition, you may make it irradiate an ultraviolet-ray, changing intensity | strength.

The amount of energy of the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably about 10 mJ / cm ² to 500 J / cm ² , and more preferably about 100 mJ / cm ² to 200 J / cm ² .

The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity thereof, but is preferably about 10 to 3600 seconds, more preferably about 10 to 600 seconds.

[2] In the assembly process, a vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, a seal material is screen-printed along at least one edge of the active matrix substrate AM and the color filter substrate CF so as to leave an injection port. Thereafter, the two substrates AM and CF are attached to each other, and the sealing material is thermally cured by heating. Next, the liquid crystal composition is injected under vacuum through the injection port into the space defined by the sealing material between the two substrates AM and CF, and then the injection port is sealed. Then, the process proceeds to [3] polymerization step.

The liquid crystal display element 1 thus obtained is preferably a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display element, and more preferably a PSA type liquid crystal display element. More preferable.

Although the liquid crystal composition and the liquid crystal display element of the present invention have been described above based on the illustrated embodiments, the present invention is not limited thereto, and each configuration is replaced with any configuration having a similar function. Alternatively, any other configuration may be added.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.

The characteristics measured for the liquid crystal composition are as follows.

Tni: Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 293K Δε: Dielectric anisotropy at 293K γ1: Rotational viscosity at 293K (mPa · s)
K11: Elastic constant of spread at 293K (pN)
K33: Elastic constant of bending at 293K (pN)

1. Preparation of liquid crystal mixture In the following, the following abbreviations are used for the description of compounds. N in the abbreviation is a natural number.

(Side chain)
-N -C _n H _{2n + 1:} linear alkyl group n- C _n H _{2n + 1} carbon atoms n -: -On linear alkyl group having a carbon number _n -OC n H _{2n + 1:} the number of carbon atoms n Linear alkoxy group

(Connection structure)
-NO- -C _n H _2n O-
(Ring structure)

The composition and physical properties of the liquid crystal mixture LC-1 are shown in Table 1 below.

2. Preparation of liquid crystal composition (Example 1)
First, the following polymerizable monomer A and the following polymerizable monomer B1 were mixed in a mass ratio of 75:25 to obtain a polymerizable monomer mixture.

Next, 0.3 part by mass of the polymerizable monomer mixture was mixed with 100 parts by mass of the liquid crystal mixture LC-1 and heated and dissolved to obtain a liquid crystal composition.

(Example 2)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer A and the polymerizable monomer B1 were mixed at a mass ratio of 50:50 to obtain a polymerizable monomer mixture. .

(Example 3)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer A and the polymerizable monomer B1 were mixed in a mass ratio of 25:75 to obtain a polymerizable monomer mixture. .

(Examples 11 to 13)
Liquid crystal compositions were obtained in the same manner as in Examples 1 to 3 except that the following polymerizable monomer B2 was used instead of the polymerizable monomer B1.

(Examples 21 to 23)
Liquid crystal compositions were obtained in the same manner as in Examples 1 to 3 except that the following polymerizable monomer B3 was used instead of the polymerizable monomer B1.

(Comparative Example 1)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer A was used alone.

(Comparative example 2)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer B1 was used alone.

(Comparative Example 3)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer B2 was used alone.

(Comparative example 4)
A liquid crystal composition was obtained in the same manner as in Example 1 except that the polymerizable monomer B3 was used alone.

3. Preparation of Liquid Crystal Display Element First, a polyimide film was applied to an ITO substrate, and then the polyimide film was rubbed to form an alignment film. Then, an empty liquid crystal cell (cell gap 3.5 μm) including an ITO substrate with an alignment film was prepared.

Next, the liquid crystal compositions of Examples and Comparative Examples were injected into an empty liquid crystal cell by a vacuum injection method.

Next, while applying a 10 V AC electric field (AC voltage) at a frequency of 100 Hz to the liquid crystal cell into which the liquid crystal composition was injected, irradiate ultraviolet rays through a filter that cuts off ultraviolet rays having a wavelength of 325 nm or less from a high pressure mercury lamp. did.

At this time, the illuminance measured under the condition of the central wavelength of 365 nm was set to be 100 mW / cm ² , and the integrated light amount of 10 J / cm ² of ultraviolet rays was irradiated. Thereby, the pretilt angle was given to the liquid crystal molecules in the liquid crystal composition.

4. Evaluation The following evaluations were performed on the liquid crystal display devices using the liquid crystal compositions of the examples and the comparative examples.

4-1. Evaluation of Pretilt Angle Providing Effect In the obtained liquid crystal display device, the pretilt angle of liquid crystal molecules was measured using a pretilt angle measuring system (“OPTIPRO” manufactured by Shintech Co., Ltd.) and evaluated according to the following criteria.

[Evaluation criteria]
A: Over 4 ° B: 2-4 °
C: less than 2 °

4-2. Evaluation of Pretilt Angle Change Amount The pretilt angle in the evaluation of "4-1" was used as the initial value.

Next, while applying a rectangular voltage of 30 V at a frequency of 100 Hz to the liquid crystal display element, light was continuously emitted from the backlight for 10 hours. After that, the pretilt angle was measured again and used as the pretilt angle (post-test value).

The value obtained by subtracting the pretilt angle (post-test value) from the measured pretilt angle (initial value) was used as the pretilt angle change amount (= absolute value of pretilt angle change) [°] and evaluated according to the following criteria.

[Evaluation criteria]
A: Change less than 0.5 ° B: Change 0.5 to 1 ° C: Change more than 1 ° As the amount of change in pretilt angle is closer to 0 [°], display failure occurs due to change in pretilt angle. Less likely.

The evaluation results are shown in Tables 2-4.

As shown in Tables 2 to 4, in each of the examples, the effect of providing the pretilt angle and the effect of reducing the change amount thereof were excellent.

On the other hand, in each comparative example, either the effect of giving the pretilt angle or the effect of reducing the amount of change was inferior.

In addition, in this example, the total polymerizable monomer was mixed in an amount of 0.3 parts by mass with respect to 100 parts by mass of liquid crystal molecules, but the present invention is not limited to this, and is in the range of 0.1 to 3 parts by mass (preferably 0 parts). It can be mixed in the range of 0.2 to 2 parts by mass). If the amount used is in such a range, the effect of the same tendency as described above can be obtained.

1 Liquid Crystal Display Element AM Active Matrix Substrate CF Color Filter Substrate 2 First Substrate 3 Second Substrate 4 Liquid Crystal Layer 5 Pixel Electrode Layer 6 Common Electrode Layer 7 First Polarizing Plate 8 Second Polarizing Plate 9 Color Filter 11 Gate Bus line 12 Data bus line 13 Pixel electrode 14 Cs electrode 15 Source electrode 16 Drain electrode 17 Contact hole

Claims

Liquid crystal molecules,
A polymerizable monomer A having a mesogen skeleton and at least two polymerizable groups bonded to the mesogen skeleton, all of the polymerizable groups being directly bonded to the mesogen skeleton;
A polymerizable monomer B having a mesogenic skeleton and at least two polymerizable groups bonded to the mesogenic skeleton, all of the polymerizable groups being bonded to the mesogenic skeleton via a spacer group. A liquid crystal composition comprising:
The liquid crystal composition according to claim 1, wherein in the polymerizable monomer A, the two polymerizable groups are bonded to substantially symmetrical positions at both ends in the long axis direction of the mesogen skeleton.
3. The liquid crystal composition according to claim 1, wherein in the polymerizable monomer A, the mesogenic skeleton has 2 to 4 ring structures.
The liquid crystal composition according to claim 3, wherein in the polymerizable monomer A, the mesogenic skeleton further includes the following substituent K i1A bonded to the ring structure.
The substituent K i1A is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched chain. Represents a cyanated alkyl group having 1 to 40 carbon atoms, or a linear or branched alkoxy group having 1 to 40 carbon atoms.
(Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X i1 ) -and / or- (CH-CN)-, and the secondary carbon atom in the alkyl group is The carbon atom is -C (= CH 2 )-, -C (= CHR i3 )-, -C (= CR i3 2 )-, -CH = CH-, -C≡C so that the oxygen atom is not directly adjacent. It may be substituted with —, —O—, —NH—, —COO— or —OCO—, and the end of the alkyl group may be substituted with OH, NH 2 or CN, wherein X i1 is , An oxygen atom, a sulfur atom, NH or NR i3 , and R i3 represents a linear or branched alkyl group having 1 to 20 carbon atoms (provided that the secondary carbon atom in the alkyl group is , Substituted with -O-, -CH = CH- or -C≡C- so that oxygen atoms are not directly adjacent May be done.).)
The liquid crystal composition according to any one of claims 1 to 4, wherein in the polymerizable monomer B, the mesogenic skeleton includes 2 to 4 ring structures.
The liquid crystal composition according to claim 5, wherein in the polymerizable monomer B, the 2 to 4 ring structures in the mesogen skeleton form a linked polycyclic structure.
The liquid crystal composition according to claim 6, wherein in the polymerizable monomer B, the mesogenic skeleton further includes the following substituent K i1B bonded to the ring structure.
The substituent K i1B is a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a linear or branched halogenated alkyl group having 1 to 40 carbon atoms, a linear or branched group. Represents a cyanated alkyl group having 1 to 40 carbon atoms, or a linear or branched alkoxy group having 1 to 40 carbon atoms.
(Two or more secondary carbon atoms in the alkyl group may be substituted with -C (= X i1 ) -and / or- (CH-CN)-, and the secondary carbon atom in the alkyl group is The carbon atom is -C (= CH 2 )-, -C (= CHR i3 )-, -C (= CR i3 2 )-, -CH = CH-, -C≡C so that the oxygen atom is not directly adjacent. It may be substituted with-, -O-, -NH-, -COO- or -OCO-, the hydrogen atom in the alkyl group may be substituted with P-Sp-, and the terminal of the alkyl group is , OH, NH 2 or CN, wherein X i1 represents an oxygen atom, a sulfur atom, NH or NR i3 , and R i3 has a linear or branched carbon atom number of 1 to 20 represents an alkyl group (provided that the secondary carbon atom in this alkyl group is directly linked to the oxygen atom). It may be substituted with -O-, -CH = CH- or -C≡C- so as not to be adjacent to each other.), P represents a polymerizable group, and Sp represents a spacer group.)
The liquid crystal composition according to any one of claims 1 to 7, wherein the amount of the polymerizable monomer A based on the total amount of the polymerizable monomer A and the polymerizable monomer B is 25 to 75% by mass.
9. The total amount of the polymerizable monomer A and the polymerizable monomer B contained in the liquid crystal composition is 0.1 to 3 parts by mass with respect to 100 parts by mass of the liquid crystal molecule. The liquid crystal composition according to any one of items.
A liquid crystal display device comprising two substrates and a liquid crystal layer provided between the two substrates and containing the liquid crystal composition according to any one of claims 1 to 9.
The liquid crystal display element according to claim 10, wherein the liquid crystal layer contains a polymerized product of the polymerizable monomer A and the polymerizable monomer B.
The liquid crystal display device according to claim 10, which is for driving an active matrix.
The liquid crystal display element according to any one of claims 10 to 12, which is a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type.