JP6733842B2 - Liquid crystal display device and method of manufacturing liquid crystal display device - Google Patents

Description

The present invention relates to a liquid crystal display element and a method for manufacturing a liquid crystal display element.

Conventionally, in a VA liquid crystal display (liquid crystal display element), a polyimide that functions as an alignment film on an electrode in order to induce vertical alignment of liquid crystal molecules when no voltage is applied and to achieve horizontal alignment of liquid crystal molecules when voltage is applied. A (PI) alignment film is provided. However, since forming a PI alignment film requires a great deal of cost, in recent years, methods for realizing alignment of liquid crystal molecules while omitting the PI alignment film have been investigated.

By the way, the surface texture of the substrate surface is also important for the orientation of liquid crystal molecules. In a liquid crystal display element provided with a PI alignment film, there is a document (for example, refer to Patent Document 1) that defines the surface roughness of the PI alignment film. However, in the liquid crystal display element in which the PI alignment film is omitted, no study has been found on the surface properties of the substrate, and there is room for study for further improvement in characteristics.

WO2008/074419

The present invention is to provide a liquid crystal display element capable of displaying an image having a high contrast, and a method for manufacturing such a liquid crystal display element.

Such an object is achieved by the present invention of the following (1) to (13).
(1) A liquid crystal display device comprising a liquid crystal layer containing liquid crystal molecules sandwiched between two substrates,
One of the substrates includes a polymer of a polymerizable monomer that is present in contact with the liquid crystal layer and that can be polymerized by irradiation with active energy rays, and the surface of the surface that contacts the liquid crystal layer due to the presence of the polymer. A liquid crystal display device having a roughness (Ra) of 1 to 30 nm.

(2) The liquid crystal display element according to (1), wherein the polymerizable monomer has a function of spontaneously aligning the liquid crystal molecules, and the alignment aid includes an alignment aid having a polar group.
(3) The liquid crystal display device according to the above (1) or (2), wherein the polymerizable monomer contains a pretilt angle forming auxiliary agent having a function of forming a pretilt angle of the liquid crystal molecules.
(4) The liquid crystal display element according to any one of (1) to (3), wherein the one substrate is a substrate that directly contacts the liquid crystal layer without an alignment film.

(5) The liquid crystal display element according to any one of (1) to (4), wherein the one substrate is a substrate including a pixel electrode.
(6) The other substrate also includes the polymer present in contact with the liquid crystal layer, and the presence of the polymer causes the surface roughness (Ra) of the surface in contact with the liquid crystal layer to be 1 to 30 nm. The liquid crystal display element according to any one of (1) to (5) above.
(7) The liquid crystal display element according to (6), wherein the other substrate is a substrate that directly contacts the liquid crystal layer without an alignment film.

(8) The liquid crystal display element according to (6) or (7), wherein the other substrate is a substrate including a color filter.
(9) The liquid crystal display device according to any one of (1) to (8), wherein the liquid crystal molecule has a negative dielectric anisotropy.
(10) The liquid crystal display element according to any one of (1) to (9) above, which is a PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type.

(11) A method for manufacturing the liquid crystal display device according to any one of (1) to (10) above,
A step of disposing the two substrates so as to face each other so as to come into contact with a liquid crystal composition containing the liquid crystal molecules and the polymerizable monomer;
And a step of polymerizing the polymerizable monomer by irradiating the active energy ray while applying an electric field to the liquid crystal composition to obtain the polymer, thereby producing a liquid crystal display device. Method.

(12) The polymerizable monomer contains an alignment aid having a function of spontaneously aligning the liquid crystal molecules,
The method for producing a liquid crystal display element according to (11) above, wherein the amount of the alignment aid contained in the liquid crystal composition is 0.1 to 3 mass %.
(13) The method for producing a liquid crystal display device according to (11) or (12), wherein the irradiation time of the active energy ray is 10 to 7200 seconds.

According to the present invention, a liquid crystal display device capable of displaying an image having high contrast can be obtained.

FIG. 3 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. It is the top view which expanded the area|region enclosed by the I line in FIG.

Hereinafter, the method for manufacturing a liquid crystal display device of the present invention will be described in detail based on preferred embodiments.
First, the liquid crystal composition used in the present invention will be described.
(Liquid crystal composition)
The liquid crystal composition contains liquid crystal molecules and an alignment aid having a function of spontaneously aligning the liquid crystal molecules and having a polar group.

((Alignment aid))
The alignment aid (spontaneous alignment compound) is a member (electrode (eg, ITO), substrate (eg, glass substrate, acrylic substrate, transparent substrate, flexible substrate, etc.)) that directly contacts the liquid crystal layer containing the liquid crystal composition, resin. Homeotropic alignment or homogeneous alignment of liquid crystal molecules contained in the liquid crystal layer by interacting with layers (for example, color filters, alignment films, overcoat layers, etc.) and insulating films (for example, inorganic material films, SiNx, etc.) It has a function to induce.

The alignment aid induces alignment of the liquid crystal molecules, a polymerizable group for polymerization, a mesogen group similar to the liquid crystal molecules, an adsorption group (polar group) capable of interacting with a member that directly contacts the liquid crystal layer. It preferably has an orientation-inducing group.

It is preferable that the adsorptive group and the orientation-inducing group are bonded to the mesogen group, and the polymerizable group is substituted for the mesogenic group, the adsorbing group and the orientation-inducing group directly or via a spacer group as necessary. The polymerizable group may be substituted with a mesogenic group while being incorporated in the adsorptive group.
Hereinafter, * at the left end and * at the right end in the chemical formulas represent a bond.

"Orientation-inducing group"
The orientation-inducing group has a function of inducing the orientation of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).

In the formula, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. However, one or more -CH ₂ in the alkyl group - without the oxygen atom directly bound, each independently, -CH = CH -, - C [identical to] C -, - O -, - It may be substituted with CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogeno group.

R ^AK1 preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and linear. It is more preferable to represent an alkyl group having 1 to 8 carbon atoms.
Further, one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or It may be substituted with -OCO-.
Further, the hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, or may be substituted with a fluorine atom.

From the viewpoint of imparting the so-called amphipathic property to the liquid crystal layer to the alignment aid, it is preferable that the alignment inducing group is bonded to the mesogen group directly or via a spacer group as necessary.

"Polymerizable group"
Polymerizable ^group, P ^{AP1 -Sp} AP1 - is preferably represented by.
P ^AP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. However, one or more -CH 2 in the alkyl group _- may be replaced by -O- or -CO-, one or more hydrogen atoms in the alkyl group are each independently Then, it may be substituted with a halogen atom or a hydroxyl group.
W ^AP1 represents a single bond, -O -, - COO- or -CH ₂ - represents a.
t ^AP1 represents 0, 1 or 2.

P ^AP1 is preferably a group represented by the following general formula (AP-1) to general formula (AP-7), and is represented by the following general formula (AP-1) or general formula (AP-2). Group represented by formula (AP-1) is more preferable.

Sp ^AP1 preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. It is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In Sp ^AP1 , one or two or more non-adjacent —CH ₂ — in the alkylene group are each independently —CH═CH—, —C≡C—, —O—, —CO—, It may be substituted with -COO- or -OCO-.

In the alignment aid, the polymerizable group ^{(P AP1 -Sp} AP1 -) number of, preferably 1 to 5 or less, more preferably 1 to 4, further not less 2 to 4 It is particularly preferably 2 or 3, and most preferably 2.
P ^AP1 -Sp ^AP1 - hydrogen atoms in the polymerizable group, may be substituted with an adsorptive group and / or orientation-induced group.

Polymerizable group ^{(P AP1 -Sp} AP1 -), the polymerizable group, mesogen group may be bonded to an adsorptive group and / or orientation-induced group.
The polymerizable group (P ^{AP1 -Sp AP1 -)} is preferably binding to the mesogenic groups, the adsorption group or orientation-induced group, and more preferably binding to the mesogenic groups or adsorptive groups.
When a plurality of P ^AP1 and/or Sp ^AP1 − are present in the molecule, they may be the same or different from each other.

"Mesogenic group"
The mesogen group means a group having a rigid portion, for example, a group having at least one cyclic group, preferably a group having 2 to 4 cyclic groups, and 3 to 4 cyclic groups. The groups provided are more preferred. In addition, if necessary, the cyclic group may be linked by a linking group. The mesogen group preferably has a skeleton similar to that of liquid crystal molecules (liquid crystal compound) used in the liquid crystal layer.
In addition, in the present specification, the “cyclic group” refers to an atomic group in which constituent atoms are cyclically bonded, and includes a carbocycle, a heterocycle, a saturated or unsaturated cyclic structure, a monocyclic and bicyclic structure, Includes polycyclic structures, aromatics, non-aromatics and the like.
Further, the cyclic group may contain at least one hetero atom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl, alkoxy, aryl etc.). When the formula group is monocyclic, the mesogenic group preferably contains two or more monocycles.

The mesogen group is preferably represented by, for example, general formula (AL).

In the formula, Z ^AL1 is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —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 -, - represents an alkylene group of OCH 2 _CH 2 O- or 1 to 20 carbon atoms. However, one or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO—.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.
One or more hydrogen atoms in Z ^AL1 , A ^AL1 and A ^AL2 may be independently substituted with a halogeno group, an adsorbing group, P ^AP1- Sp ^AP1 -or a monovalent organic group. ,
When a plurality of Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different from each other.
m ^AL1 represents an integer of 1 to 5.

In general formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and a single bond. , - _{(CH 2) 2} - or - _{(CH 2) 4} - and still more preferably a. One or not adjacent two or more _-CH 2 in the alkylene group - is, -O -, - COO- or may be substituted with -OCO-.
Furthermore, when it is intended to increase the linearity of a rod-shaped molecule, Z ^AL1 is a single bond in which rings are directly connected to each other, or an even number of atoms directly connecting the rings is even. The form is preferred. For example, in the case of —CH ₂ —CH ₂ COO—, the number of atoms that directly connect the rings is four.

In formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. As the divalent cyclic group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo(2,2,2)octylene group, decahydronaphthalene-2,6-diyl group , Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a- Octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b: 4,5-b']diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene It is preferably one kind selected from the group consisting of -2,7-diyl group and fluorene-2,7-diyl group, and is 1,4-phenylene group, 1,4-cyclohexylene group, 2,6- A naphthylene group or a phenanthrene-2,7-diyl group is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is further preferable.
In addition, these groups may be unsubstituted or substituted with a substituent. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.
Further, one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorption group, P ^AP1- Sp ^AP1 -or a monovalent organic group.

In the general formula (AL), the monovalent organic group is a group having a chemical structure formed by the organic compound being in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. An atomic group.
Examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy having 2 to 15 carbon atoms. Groups, etc., preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Is more preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms or 1 to 2 carbon atoms. An alkoxy group is particularly preferable, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferable.
Further, one or two or more non-adjacent —CH ₂ — in the above alkyl group, alkenyl group, alkoxy group, alkenyloxy group may be substituted with —O—, —COO— or —OCO—. Further, the monovalent organic group may have a role as an orientation-inducing group described later.
In the general formula (AL), m ^AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

The following formulas (me-1) to (me-45) may be mentioned as preferred forms of the mesogen group.

The general formula (AL) has a structure in which two hydrogen atoms are eliminated from these compounds.
In these formulas (me-1) to (me-45), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are each independently a halogeno group, P ^AP1-Sp^AP1-It may be substituted with a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group or an orientation inducing group.

Among the above mesogen groups, preferred forms are formulas (me-8) to (me-45), and more preferred forms are formulas (me-8) to (me-10) and formulas (me-12) to (me-12). (Me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-45), and more preferable forms. Are expressions (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36). ~ (Me-37), (me-42) to (me-45).

Among the above mesogen groups, a particularly preferable form is the following general formula (AL-1) or (AL-2), and a most preferable form is the following general formula (AL-1).

In the formula, X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 each independently represent a hydrogen atom, a halogeno group, P ^AP1- Sp ^AP1- , an adsorption group or an orientation-inducing group.
Ring ^{A AL11,} Ring ^{A AL12} and ring ^{A AL21} each independently represent a cyclohexane ring or a benzene ring.
Any one type or two or more types of X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 are substituted with an adsorption group.
Any one kind or two or more kinds of X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 are substituted with an orientation-inducing group.
Adsorptive group and orientation derivative ^groups, P ^{AP1 -Sp} AP1 - may be substituted with.
Formula (AL-1) or general formula (AL-2) is, ^P AP1 ^{-Sp APL} in the molecule - has one or more.

In the general formula (AL-1), X^AL101Is preferably an orientation-inducing group.
In the general formula (AL-1), X^AL109, X^AL110And X^AL111It is preferred that at least one of the^AL109And X^AL110Are both adsorbing groups or X^AL110Is more preferably an adsorption group, and X is^AL110Is more preferably an adsorptive group.
In the general formula (AL-1), X^AL109, X^AL110And X^AL111At least one of P^AP1-Sp^AP1-Or an adsorptive group having a polymerizable site in the structure, X^AL109And X^AL111Both or one of P^AP1-Sp^AP1It is more preferable that it is −.
In the general formula (AL-1), X^AL104~ X^AL108, X^AL112~ X^{AL1 16}1 or 2 each independently is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogeno group, and an alkyl group having 1 to 3 carbon atoms or fluorine. More preferably, it is an atom. Especially X^AL105, X^AL106Or X ^AL107Are preferably each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

In the general formula (AL-2), X^AL201Is preferably an orientation-inducing group.
In the general formula (AL-2), X^AL207, X^AL208And X^AL209It is preferred that at least one of the^AL207And X^AL208Are both adsorbing groups or X^AL208Is more preferably an adsorption group, and X is^AL208Is more preferably an adsorptive group.
In the general formula (AL-2), X^AL207, X^AL208And X^AL209At least one of P^AP1-Sp^AP1-Or an adsorptive group having a polymerizable site in the structure, X^AL207And X^AL209Both or one of P^AP1-Sp^AP1It is more preferable that it is −.
In the general formula (AL-2), X^AL202~ X^AL206, X^AL210~ X^{AL2 14}1 or 2 each independently is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogeno group, and an alkyl group having 1 to 3 carbon atoms or fluorine. More preferably, it is an atom. Especially X^AL204, X^AL205Or X ^AL206Are preferably each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

"Adsorption group"
The adsorbing group is a group having a role of adsorbing an adsorbent which is a layer that comes into contact with the liquid crystal composition such as a substrate, a film and an electrode.
Adsorption is generally classified into chemisorption in which a chemical bond (covalent bond, ionic bond, or metal bond) is formed to adsorb between an adsorbent and an adsorbate, and physical adsorption other than chemisorption. In the present specification, the adsorption may be either chemical adsorption or physical adsorption, but physical adsorption is preferable. Therefore, the adsorption group is preferably a group capable of physically adsorbing to the adsorption medium, and more preferably a group capable of binding to the adsorption medium by intermolecular force.
Examples of the form of binding to the adsorbent medium by intermolecular force include a form of interaction such as permanent dipole, permanent quadrupole, dispersive force, charge transfer force or hydrogen bond.
A preferable form of the adsorbing group is a form capable of binding to the adsorbent by hydrogen bonding. In this case, the adsorbing group may serve as either a donor or an acceptor of protons that mediate hydrogen bonding, or may serve as both.

The adsorptive group is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked (hereinafter, the “adsorptive group” is also referred to as a “polar group”). In the present specification, the polar element refers to an atomic group in which a carbon atom and a hetero atom are directly linked.
The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. Is more preferable, at least one selected from the group consisting of N and O is more preferable, and O is particularly preferable.

In the orientation aid, the valence of the polar element is not particularly limited, such as monovalent, divalent, and trivalent, and the number of polar elements in the adsorbing group is not particularly limited.
The alignment aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.
Incidentally, the adsorption group, excluding a polymerizable group and orientation induced group, a hydrogen atom in the adsorption group ^{P AP} 1 ^{-Sp AP1} - hydrogen atoms in - structure and ^P AP1 ^{-Sp AP1} which substituted by - The structure substituted with OH is contained in the adsorption group.

The adsorptive group contains one or more polar elements and is roughly classified into a cyclic group type and a chain group type.
The cyclic radical type is a form containing a cyclic group having a cyclic structure containing a polar element in its structure, and the chain radical type is a cyclic group having a cyclic structure containing a polar element in its structure. It is a form that does not include.
The chain group type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure which does not include a polar element in a part thereof.

The cyclic group-type adsorptive group means a form having a structure containing at least one polar element in a cyclic atomic arrangement.
In addition, in this specification, the cyclic group is as described above. Therefore, the cyclic group-type adsorptive group only needs to include a cyclic group containing a polar element, and the entire adsorptive group may be branched or linear.

On the other hand, a chain-type adsorptive group is a structure that does not include a cyclic atomic array containing polar elements in the molecule and contains at least one polar element in a linear atomic array (which may be branched). Means a form having.
In addition, in the present specification, the chain group refers to an atomic group in which the constituent atoms are linearly (may be branched) bonded to each other without including a cyclic atomic array in the structural formula, and are acyclic. Refers to the group. In other words, the chain group means a linear or branched aliphatic group, and may contain either a saturated bond or an unsaturated bond.
Thus, chain groups include, for example, alkyl, alkenyl, alkoxy, ester, ether or ketone and the like. The hydrogen atom in these groups may be substituted with at least one substituent (reactive functional group (vinyl group, acryl group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.)). .. The chain group may be linear or branched.

The cyclic group-type adsorbing group may be a heteroaromatic group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring). A heteroaromatic group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring) is more preferable, and a 5-membered ring hetero group. It is more preferably an aromatic group, a 5-membered heteroalicyclic group, a 6-membered heteroaromatic group or a 6-membered heteroalicyclic group. In addition, the hydrogen atom in these ring structures may be substituted with a halogeno group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkyloxy group.

The chain group-type adsorptive group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in which hydrogen atom in the structure or —CH ₂ — is substituted with a polar element. It should be noted that one or two or more non-adjacent —CH ₂ — in the alkyl group are substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. May be done. In addition, the chain-type adsorptive group preferably contains one or more polar elements at the ends thereof.

A hydrogen atom in the adsorptive group may be replaced with a polymerizable group.
Specific examples of the polar element include a polar element containing an oxygen atom (hereinafter referred to as an oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter referred to as a nitrogen-containing polar element), a polar element containing a phosphorus atom (hereinafter referred to as a phosphorus-containing polar element). Element), a polar element containing a boron atom (hereinafter, boron-containing polar element), a polar element containing a silicon atom (hereinafter, silicon-containing polar element), or a polar element containing a sulfur atom (hereinafter, sulfur-containing polar element). .. From the viewpoint of adsorption ability, the polar element is preferably a nitrogen-containing polar element, a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.

As the oxygen-containing polar element, at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group or the group is a carbon atom. It is preferably a group linked to an atom.
As the nitrogen-containing polar element, at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group, and a ureido group, or the group is a carbon atom. It is preferably a group linked to an atom.
The phosphorus-containing polar element is preferably at least one group selected from the group consisting of phosphinyl groups and phosphoric acid groups, or a group in which the group is linked to a carbon atom.

Therefore, as the adsorption group, a cyclic group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, nitrogen-containing cyclic group), a sulfur-containing polar group A cyclic group having an element (hereinafter, a sulfur-containing cyclic group), a chain group having an oxygen-containing polar element (hereinafter, an oxygen-containing chain group), and a chain group having a nitrogen-containing polar element (hereinafter, It is preferable to include one or more groups selected from the group consisting of (nitrogen-containing chain group) itself or the group, and from the viewpoint of adsorption ability, an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing cyclic group. It is more preferable to contain one or more groups selected from the group consisting of a chain group and a nitrogen-containing chain group.

The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as an ether group in the ring structure.

The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as a carbonyl group, a carbonate group and an ester group in the ring structure.

The nitrogen-containing cyclic group preferably contains any of the following groups.

The oxygen-containing chain group preferably contains any of the following groups.

Where R^at1Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Z^at1Represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. However, -CH in the alkylene group or alkenylene group_Two-May be substituted with -O-, -COO-, -C(=O)-, or -OCO- so that oxygen atoms are not directly adjacent to each other.
X^at1Represents an alkyl group having 1 to 15 carbon atoms. However, -CH in the alkyl group _Two-May be substituted with -O-, -COO-, -C(=O)-, or -OCO- so that oxygen atoms are not directly adjacent to each other.

式中、Ｒ^ａｔ、Ｒ^ｂｔ、Ｒ^ｃｔ及びＲ^ｄｔは、それぞれ独立して、水素原子又は炭素原子数１〜５のアルキル基を表す。 The nitrogen-containing chain group preferably contains any of the following groups.

In the formula, R ^at , R ^bt , R ^ct, and R ^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

式中、Ｓｐ^ＡＴ１は、単結合、炭素原子数１〜２５の直鎖状若しくは分岐状のアルキレン基を表す。ただし、アルキレン基中の水素原子は、−ＯＨ、−ＣＮ、−Ｗ^ＡＴ１−Ｚ^{Ａ Ｔ１}又はＰ^ＡＰ１−Ｓｐ^ＡＰ１−で置換されてもよく、アルキレン基中の−ＣＨ_２−は、酸素原子が直接結合しないように環式基、−Ｏ−、−ＣＯＯ−、−Ｃ（＝Ｏ）−、−ＯＣＯ−、−ＣＨ＝ＣＨ−で置換されてもよい。
Ｗ^ＡＴ１は、単結合又は下記一般式（ＷＡＴ１）又は（ＷＡＴ２）を表す。
Ｚ^ＡＴ１は、極性要素を含む１価の基を表す。ただし、Ｚ^ＡＴ１中の水素原子は、−ＯＨ、−ＣＮ、−Ｓｐ^ＡＴ１−Ｗ^ＡＴ１−Ｚ^ＡＴ１又はＰ^ＡＰ１−Ｓｐ^ＡＰ１−で置換されてもよい。 The adsorptive group is preferably a group represented by the following general formula (AT).

In the formula, Sp ^AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atoms in the alkylene ^{group, -OH, -CN, -W AT1 -Z} A T1 or ^P AP1 ^{-Sp AP1} - may be substituted with, -CH ₂ in the alkylene group - is an oxygen atom It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, or -CH=CH- so as not to be directly bonded.
W ^AT1 represents a single bond or the following general formula (WAT1) or (WAT2).
Z ^AT1 represents a monovalent group containing a polar element. ^However, the hydrogen atoms in ^{Z AT1 is, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with.

（式中、Ｓｐ^ＷＡＴ１及びＳｐ^ＷＡＴ２は、それぞれ独立して、単結合、炭素原子数１〜２５の直鎖状若しくは分岐状のアルキレン基を表し、アルキレン基中の水素原子は、−ＯＨ、−ＣＮ、−Ｓｐ^ＡＴ１−Ｗ^ＡＴ１−Ｚ^ＡＴ１又はＰ^ＡＰ１−Ｓｐ^ＡＰ１−で置換されてもよく、アルキレン基中の−ＣＨ_２−は、酸素原子が直接結合しないように環式基、−Ｏ−、−ＣＯＯ−、−Ｃ（＝Ｏ）−、−ＯＣＯ−又は−ＣＨ＝ＣＨ−で置換されてもよい。）

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and a hydrogen atom in the alkylene group is -OH, -. CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 — may be substituted, and —CH ₂ — in the alkylene group is a cyclic group, —O— so that an oxygen atom is not directly bonded. , -COO-, -C(=O)-, -OCO- or -CH=CH-.)

Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 each independently preferably represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear carbon atom number. It is more preferable to represent an alkylene group having 1 to 20 carbon atoms, and it is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 , one or two or more non-adjacent —CH ₂ — in the alkylene group are each independently —CH═CH so that an oxygen atom is not directly bonded. It may be substituted with -, -C≡C-, -O-, -CO-, -COO- or -OCO-.
The ^hydrogen atoms in ^{Sp AT1} and ^{Sp WAT1} are each ^{independently,} -Sp ^AT1 -W ^{AT1 -Z AT1} or ^P AP1 ^{-Sp AP1} - it may be substituted with.

Z ^AT1 represents a monovalent group containing a polar element and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atoms in the alkylene ^{group, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with, -CH in the alkylene radical ₂ -, oxygen It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that the atoms are not directly adjacent.
Z ^ZAT11 represents a group containing a polar element.
The structure represented by the ring containing Z ^ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring.
Z ^ZAT11 and hydrogen atoms in ^{Z ZAT12 is, -OH, -CN, -Sp AT1 -W} A T1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with.

R ^ZAT11 and R ^ZAT12 each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms. However, the hydrogen atoms in the alkyl ^{group, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with, -CH in the alkyl group ₂ -, oxygen It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that the atom is not directly bonded.

The group represented by general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).

In the formula, a hydrogen atom bonded to a carbon atom is -OH, -CN, -Sp.^AT1-W^AT1-Z ^AT1Or P^AP1-Sp^AP1It may be replaced with -.
Sp^ZAT11Represents a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group is -OH, -CN, -Sp.^AT1-W^AT1-Z ^AT1Or P^AP1-Sp^AP1-CH in the alkylene group, which may be substituted with-_Two-May be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that oxygen atoms are not directly adjacent to each other.

R ^ZAT11 represents a linear or branched alkyl group having 1 to 8 carbon atoms. However, the hydrogen atoms in the alkyl ^{group, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with, -CH in the alkyl group ₂ -, oxygen It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that the atom is not directly bonded.

The group represented by general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).

In the formula, the hydrogen atom bonded to the carbon atom is a halogen atom, -OH, -CN, -Sp.^AT1-W^AT1-Z^AT1Or P^AP1-Sp^AP1It may be replaced with -.
Sp^ZAT11Represents a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group is -OH, -CN, -Sp.^AT1-W^AT1-Z ^AT1Or P^AP1-Sp^AP1-CH in the alkylene group, which may be substituted with-_Two-May be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that oxygen atoms are not directly adjacent to each other.

Examples of the group represented by formula (ZAT1-1) include the groups below.

Where R^tcIs a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P^AP1-Sp^{AP 1}Represents -. However, the hydrogen atom in the alkyl group is -OH, -CN, -Sp.^AT1-W^{A T1}-Z^AT1Or P^AP1-Sp^AP1-CH in the alkyl group, which may be substituted with -CH _Two-May be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that oxygen atoms are not directly adjacent to each other.
The hydrogen atom in the molecule is P^AP1-Sp^AP1It may be replaced with -.
* Represents a bond.

The orientation aid is preferably in a form in which the polar element contained in the adsorptive group or the polar element contained in the polymerizable group is localized. The adsorptive group is an important structure for vertically aligning liquid crystal molecules, and when the adsorptive group and the polymerizable group are adjacent to each other, a better alignment property can be obtained, and a favorable liquid crystal composition can be obtained. Shows solubility.
Specifically, the orientation aid is preferably in a form having a polymerizable group and an adsorptive group on the same ring of the mesogen group. In such a form, one or more polymerizable groups and one or more adsorbing groups are respectively bonded on the same ring, and at least one of the one or more polymerizable groups or at least one of the one or more adsorbing groups. Of these, a form in which one is bonded to the other and has a polymerizable group and an adsorptive group on the same ring is included.
Further, in this case, a hydrogen atom in the spacer group of the polymerizable group may be replaced with an adsorptive group, and further, a hydrogen atom in the adsorptive group may be replaced with a polymerizable group through the spacer group. Good.

The orientation aid is preferably a compound represented by the following general formula (SAL).

In the formula, the hydrogen atom bonded to the carbon atom is a linear or branched alkyl group having 1 to 25 carbon atoms, -OH, -CN, -Sp ^AT1- W ^AT1- Z ^AT1 or P ^AP1- Sp ^{A. It} may be substituted with ^P1- . However, the hydrogen atoms in the alkyl ^{group, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with, -CH in the alkyl group ₂ -, oxygen It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that the atom is not directly bonded.
R ^AK1 has the same meaning as R ^AK1 in formula (AK).

A^AL1And A^AL2Are each independently A in the general formula (AL).^AL1And A ^AL2Means the same as.
Z^AL1Is Z in general formula (AL)^AL1Means the same as.
m^AL1Is m in the general formula (AL)^AL1Means the same as.
Sp^AT1Is Sp in the general formula (AT).^AT1Means the same as.
W^AT1Is W in the general formula (AT)^AT1Means the same as.
Z^AT1Is Z in the general formula (AT)^AT1Means the same as.

The compound represented by the general formula (SAL) is preferably a compound represented by the following formulas (SAL-1.1) to (SAL-2.9).

The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 50% by mass. The more preferable lower limit values thereof are 0.05% by mass and 0.1% by mass from the viewpoint of aligning the liquid crystal molecules more preferably. On the other hand, the more preferable upper limit values thereof are 30% by mass, 10% by mass, 7% by mass, 5% by mass, 4% by mass and 3% by mass from the viewpoint of improving response characteristics.

((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. However, any one or not adjacent two or more -CH ₂ present in the alkyl group - is, -CH = CH -, - C≡C -, - O -, - CO -, - COO- or - It may be replaced with OCO-.
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 this group may be substituted with —O—),
(B) 1,4-phenylene group (any one or two or more non-adjacent -CH= present in this 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 of those present in these groups) One or two or more non-adjacent two or more -CH= may be substituted with -N=), and (d) represents a group selected from the group consisting of 1,4-cyclohexenylene group, Each of the group (a), the group (b), the group (c) and the group (d) may be independently 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 = N-N = CH -, - CH = CH -, - CF = CF- or -C≡C- the Represent
X ^N21 represents a hydrogen atom or a fluorine atom.
T ^N31 is, -CH ₂ - represents an or oxygen atom.
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 +n ^N12 , n ^N21 +n ^N22 and n ^N31 +n ^N32 are respectively Independently, 1, 2 or 3.
When each of n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 is 2 or more, A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 may be the same or different from each other. ..

The compound represented by any of the general formulas (N-1) to (N-3) has a negative dielectric anisotropy (Δε), and its absolute value is preferably larger than 3.
R ^{N11 to} R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. An alkenyloxy group is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is more preferable. , An alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is particularly preferable, and carbon Most preferred is an alkenyl group having 3 atoms (ie, a propenyl group).

When the ring structure to which they are bonded is a benzene ring (aromatic ring), R^N11~ R ^N32Are independently preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms.
When the ring structure to which they are bonded is a saturated ring structure such as a cyclohexane ring, a pyran ring or a dioxane ring, R^N11~ R^N32Are 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 alkenyl group having 2 to 5 carbon atoms. preferable.
In order to stabilize the nematic phase, R^N11~ R^N32Independently, the total of carbon atoms and oxygen atoms (when present) is preferably 5 or less, and linear is also preferable.

各式中、黒点は結合手を表す。 The alkenyl group is preferably a group selected from the group represented by the following formulas (R1) to (R5).

In each formula, a black dot represents a bond.

A ^{N11 to} A ^N32 are each independently preferably an aromatic group when increasing the refractive index anisotropy (Δn) of liquid crystal molecules, and an aliphatic group when improving the response speed of the liquid crystal molecules.
Examples of the aromatic group or aliphatic group include trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group. , 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo[2.2.2]octylene group , Piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferable. The structure represented by the following chemical formula 40 is more preferable, and a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group is further preferable.

Z ^N11 to Z ^N32 are each _{independently, -CH 2 O -, - CF} 2 O -, - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond are preferred, _-CH 2 O -, - CH ₂ CH ₂ - or a single bond is more preferable, _-CH 2 O-or a single bond is particularly preferred.
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 each independently preferably 1 or 2, and a combination in which n ^N11 is 1 and n ^N12 is 0, n ^{N1 1} is 2 and n ^N12 is 0. A combination in which n ^N11 is 1 and n ^N12 is 1, a combination in which n ^N11 is 2 and n ^N12 is 1, a combination in which n ^N21 is 1 and n ^N22 is 0, n ^N21 is 2 and n ^N22 Is 0, a combination in which n ^N31 is 1 and n ^N32 is 0, and a combination in which n ^N31 is 2 and n ^N32 is 0 are more preferable.

The amounts of the compounds represented by 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 amounts of the compounds represented by the general formulas (N-1) to (N-3) have 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, it is preferable that the lower limit and the upper limit of the amount be low. Further, in order to keep the driving voltage of the liquid crystal display element low, when the dielectric anisotropy (Δε) of the liquid crystal composition is increased, it is preferable that the amount be high in the lower limit and high in the upper limit.

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

In the formula, R ^N11 and R ^N12 have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
n ^Na11 , n ^Nb11 , n ^Nc11 and n ^Nd11 each independently represent 0 to 2.
n ^Ne11 , n ^Nf11 and n ^Ng11 each independently represent 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.

In the general formulas (N-1a) to (N-1g), n ^Na11 preferably represents 0 or 1. It is preferable that n ^Nb11 represents 1 or 2. It is preferable that n ^Nc11 represents 0 or 1. n ^Nd11 preferably represents 1 or 2. n ^Ne11 preferably represents 1 or 2. n ^Nf12 preferably represents 1 or 2. n ^Ng11 preferably represents 1 or 2. Further, in the general formulas (N-1e) and (N-1g), the plurality of A ^Ne11 , Z ^Ne11 , and/or A ^Ng11 existing in the molecule may be the same or different.

More specifically, the compounds represented by the general formula (N-1) are represented by the following general formulas (N-1-1) to (N-1-5) and general formulas (N-1-10) to (N-1-10). N-1-18) or compounds represented by general formulas (N-1-20) to (N-1-22) are preferred.

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

In the formula, R ^N111 and R ^N112 have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
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 compounds represented by formula (N-1-1) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-1) contained in the liquid crystal composition 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. %, 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 %.

In addition, when the improvement of Δε is important, it is preferable to set the amount of the compound represented by the general formula (N-1-1) to a higher amount, and when the solubility at low temperature is important, the amount thereof is set. If the amount is set to a large amount, the effect is high, and if Tni is important, the amount is set to be small, the effect is high. Furthermore, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-1) to the middle of the above range.

The compound represented by the general formula (N-1-1) has the following formulas (N-1-1.1) to (N-1-1.4) and formulas (N-1-1.11) to (N-1-1. (N-1-1.14) or (N-1-1.20) to (N-1-1.22) are preferred, and compounds represented by formula (N-1-1. The compound represented by (N-1-1.4) is more preferable, and the compound represented by formula (N-1-1.1) or (N-1-1.3) is preferable. More preferable.

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

In the formula, R ^N121 and R ^N122 have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
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 or a propoxy group. Is more preferable.

The compounds represented by general formula (N-1-2) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable 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 mass %, 35 mass %, 37 mass %, 40 mass %, 42 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 %.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-2) to a higher amount, and when importance is attached to the solubility at low temperature, the amount is changed. If the amount is set small, the effect is high. If the Tni is important, the amount is set large, and the effect is high. Furthermore, in the case of improving the drop mark and the burn-in property, it is preferable to set the amount of the compound represented by the general formula (N-1-2) to the middle of the above range.

The compound represented by the general formula (N-1-2) has the following formulas (N-1-2.1) to (N-1-2.7) and formulas (N-1-2.10) to (N-1-2.10). N-1-2.13) or compounds represented by formulas (N-1-2.20) to (N-1-2.22) are preferred, and compounds represented by formula (N-1-2.3) are also preferred. To (N-1-2.7), formula (N-1-2.10), formula (N-1-2.11), formula (N-1-2.13) or formula (N-1-). The compound represented by 2.20) is more preferable.

When importance is attached to the improvement of Δε, the compounds represented by formulas (N-1-2.3) to (N-1-2.7) are preferable. When the improvement of Tni is emphasized, it is a compound represented by the formula (N-1-2.10), the formula (N-1-2.11) or the formula (N-1-2.13). preferable. Further, when importance is attached to the improvement of response speed, the compound represented by the formula (N-1-2.20) is preferable.

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

In the formula, R ^N131 and R ^N132 have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
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 a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group. More preferable.

The compounds represented by general formula (N-1-3) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-3) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-3) to a high value, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-3) to the middle of the above range.

The compound represented by the general formula (N-1-3) is represented by the following formulas (N-1-3.1) to (N-1-3.7), formula (N-1-3.10), formula The compound represented by formula (N-1-3.11), formula (N-1-3.20) or formula (N-1-3.21) is preferable, and the compound represented by formula (N-1-3. 1) to (N-1-3.7) or compounds represented by formula (N-1-3.21) are more preferable, and formulas (N-1-3.1) to (N-1) are preferred. -3.4) or a compound represented by the formula (N-1-3.6) is more preferable.

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

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

^{Wherein, R N141} and ^{R N142} are respectively the same meanings 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, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5 preferably a methyl group, a propyl group, An ethoxy group or a butoxy group is more preferable.

The compounds represented by formula (N-1-4) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-4) 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, 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.

In addition, when the improvement of Δε is emphasized, it is preferable to set the amount of the compound represented by the general formula (N-1-4) to a higher amount, and when the solubility at low temperature is important, the amount thereof is set. If the amount is set to a large amount, the effect is high, and if Tni is important, the amount is set to be small, the effect is high. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-4) to the middle of the above range.

The compound represented by the general formula (N-1-4) has the following formulas (N-1-4.1) to (N-1-4.4) or formulas (N-1-4.11) to (N-1-4.11). N-1-4.14) is preferable, and compounds represented by formulas (N-1-4.1) to (N-1-4.4) are more preferable. More preferably, it is a compound represented by the formula (N-1-4.1), the formula (N-1-4.2) or the formula (N-1-4.4).

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

In the formula, R ^N151 and R ^N152 have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
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, a propyl group or A butyl group is more preferred.

The compounds represented by general formula (N-1-5) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-5) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-5) to a high amount, and when importance is attached to the solubility at low temperature, the amount is changed. If the amount is set small, the effect is high. If the Tni is important, the amount is set large, and the effect is high. Furthermore, in the case of improving the dripping trace and the burn-in property, it is preferable to set the amount of the compound represented by the general formula (N-1-5) to the middle of the above range.

The compound represented by the general formula (N-1-5) is preferably a compound represented by the following formulas (N-1-5.1) to (N-1-5.6), More preferably, it is a compound represented by N-1-5.1), formula (N-1-5.2) or formula (N-1-5.4).

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

In the formula, R ^N1101 and R ^N1102 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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.
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 more preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-10) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-10) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-10) to be high, and when importance is attached to the solubility at low temperature, the amount thereof is set. The higher the effect is, the higher the effect is. When the Tni is important, the higher the effect is, the higher the effect is. Furthermore, in the case of improving the dripping trace and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-10) to an intermediate value within the above range.

The compound represented by the general formula (N-1-10) includes compounds represented by the following formulas (N-1-10.1) to (N-1-10.5) or formulas (N-1-1.01) to (N--10.11). N-1-10.14) are preferred, and compounds represented by formulas (N-1-10.1) to (N-1-10.5) are more preferred. The compound represented by formula (N-1-10.1) or formula (N-1-10.2) is more preferred.

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

In the formula, R ^N1111 and R ^N1112 represent the same meaning as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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.
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 more preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-11) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-11) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-11) to be high, and when importance is attached to the solubility at low temperature, the amount thereof is set. The effect is high when the value is set low, and the effect is high when the amount is set high when Tni is important. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-11) to the middle of the above range.

The compound represented by the general formula (N-1-11) is represented by the following formulas (N-1-11.1) to (N-1-11.5) or formulas (N-1-11.11) to (N--11.11). N-1-11.14) is preferable, and compounds represented by formulas (N-1-11.1) to (N-1-11.5) are more preferable. More preferably, it is a compound represented by formula (N-1-11.2) or formula (N-1-11.4).

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

In the formula, R ^N1121 and R ^N1122 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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 more preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-12) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-12) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-12) to a high amount, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-12) to the middle of the above range.

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

In the formula, R ^N1131 and R ^N1132 represent the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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 more preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by the general formula (N-1-13) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-13) contained in the liquid crystal composition 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.

In addition, when the improvement of Δε is important, it is preferable to set the amount of the compound represented by the general formula (N-1-13) to a higher amount, and when the solubility at low temperature is important, the amount thereof is set. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the amount of the compound represented by the general formula (N-1-13) to the middle of the above range.

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

In the formula, R ^N1141 and R ^N1142 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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 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 more preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-14) may be used alone, or may be used in combination of two or more kinds. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-14) contained in the liquid crystal composition 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.

In addition, when the improvement of Δε is emphasized, it is preferable to set the amount of the compound represented by the general formula (N-1-14) to a higher amount, and when the solubility at low temperature is important, the amount thereof is set. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the burn-in property, it is preferable to set the amount of the compound represented by the general formula (N-1-14) to the middle of the above range.

The compound represented by formula (N-1-15) is the following compound.

In the formula, R ^N1151 and R ^N1152 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
R ^N1151 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 ^N1152 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, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-15) may be used alone, or may be used in combination of two or more kinds. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-15) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-15) to a higher value, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-15) to the middle of the above range.

The compound represented by formula (N-1-16) is the following compound.

In the formula, R ^N1161 and R ^N1162 represent the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
R ^N1161 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 ^N1162 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, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-16) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-16) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-16) to a higher amount, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Furthermore, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-16) to the middle of the above range.

The compound represented by formula (N-1-17) is the following compound.

In the formula, R ^N1171 and R ^N1172 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
R ^N1171 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 ^N1172 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, a propoxy group or a butoxy group.

The compounds represented by formula (N-1-17) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-17) contained in the liquid crystal composition 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.

In addition, when the improvement of Δε is important, it is preferable to set the amount of the compound represented by the general formula (N-1-17) to a higher amount, and when the solubility at low temperature is important, the amount thereof is set. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-17) to the middle of the above range.

The compound represented by the general formula (N-1-18) is the following compound.

In the formula, R ^N1181 and R ^N1182 have the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
R ^N1181 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 ^N1182 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, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-18) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-18) contained in the liquid crystal composition 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.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-18) to a higher amount, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-18) to the middle of the above range.

The compound represented by the general formula (N-1-18) is preferably a compound represented by the following formulas (N-1-18.1) to (N-1-18.5), The compounds represented by formulas (N-1-18. 1) to (N-1-18. 3) are more preferable, and the compounds of formula (N-1-18. 2) or formula (N-1-18. 3) are also preferable. It is more preferable that the compound is

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

In the formula, R ^N1201 and N ¹²⁰² have the same meanings as R ^N11 and R ^N12 in the general formula (N-1), respectively.
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.

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

The amount of the compound represented by formula (N-1-20) contained in the liquid crystal composition 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.

When importance is attached to the improvement of Δε, the amount of the compound represented by the general formula (N-1-20) is preferably set higher, and when importance is attached to the solubility at low temperatures, the amount is increased. The effect is high when set, and when Tni is emphasized, the effect is high when the amount is set to be large. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-20) to the middle of the above range.

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

^Each of R ^N1211 and R ^N1212 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.

The compounds represented by formula (N-1-21) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by General Formula (N-1-21) contained in the liquid crystal composition 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.

When importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-21) to a higher amount, and when importance is attached to the solubility at low temperature, the amount is increased. The effect is high when set, and when Tni is emphasized, the effect is high when the amount is set to be large. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-21) to the middle of the above range.

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

In the formula, R ^N1221 and R ^N1222 represent the same meanings as R ^{N1 1} and R ^N12 in the general formula (N-1), respectively.
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.

The compound represented by the general formula (N-1-22) may be used alone, or may be used in combination of two or more kinds. The type of compound to be combined 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.

The amount of the compound represented by formula (N-1-22) 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 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, 5% by mass. %.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-1-22) to a high value, and when importance is attached to the solubility at low temperature, the amount is changed. If a large amount is set, the effect is high. If Tni is important, a large amount is effective. Further, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (N-1-21) to the middle of the above range.

The compound represented by the general formula (N-1-22) includes compounds represented by the following formulas (N-1-22.1) to (N-1-22.6), formula (N-1-22.11) or (N-1-22.11). It is preferable that it is a compound represented by N-1-22.12), and it is more preferable that it is a compound represented by a formula (N-1-22. 1)-(N-1-22.5). Compounds represented by formulas (N-1-22.1) to (N-1-22.4) are more preferable.

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

In the formula, R ^N321 and R ^N322 have the same meanings as R ^N31 and R ^N32 in the general formula (N-3), respectively.
R ^N321 and R ^N322 are 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 or a pentyl group.

The compound represented by formula (N-3-2) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (N-3-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 3% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% 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% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass and 5% by mass.

In addition, when importance is attached to the improvement of Δε, it is preferable to set the amount of the compound represented by the general formula (N-3-2) to a higher amount, and when importance is attached to the solubility at low temperature, the amount is changed. If the amount is set to a large amount, the effect is high, and if Tni is important, the amount is set to be small, the effect is high. Furthermore, in the case of improving the drop mark and the image sticking property, the amount of the compound represented by the general formula (N-3-2) is preferably set in the middle of the above range.

The compound represented by the general formula (N-3-2) is preferably a compound represented by the following formulas (N-3-2.1) to (N-3-2.3).

The liquid crystal molecule may further contain a compound represented by the following general formula (L).

In the formula, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms. However, any one or not adjacent two or more -CH ₂ present in the alkyl group - are each independently, -CH = CH -, - C≡C -, - O -, - CO-, It may be substituted with -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 this group may be substituted with —O—),
(B) 1,4-phenylene group (any one or two or more non-adjacent -CH= present in this 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 these groups or not adjacent Two or more -CH= may be substituted with -N=.)
The group (a), the group (b) and the group (c) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom.

Z^L1And Z^L2Are each independently a single bond, -CH_TwoCH_Two-, -(CH_Two) _Four-, -OCH_Two-, -CH_TwoO-, -COO-, -OCO-, -OCF_Two-, -CF_TwoRepresents O-, -CH=NN-CH-, -CH=CH-, -CF=CF- or -C≡C-.
n^L1If is 2 or more, A^L2And Z^L2May be the same or different from each other, but exclude the compounds represented by the general formulas (N-1) to (N-3).

The compound represented by the general formula (L) corresponds to a dielectrically almost neutral compound (Δε value is −2 to 2). These compounds may be used alone or in combination. The type of compound to be combined 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 types of compounds used are, for example, 1 type, 3 types, 4 types, 5 types, 6 types, 7 types, 8 types, 9 types, and 10 types. More than type.

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.
Its preferable 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, It is 80 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 keeping the viscosity (η) of the liquid crystal composition low and increasing the response speed, the amount of the compound represented by the general formula (L) preferably has a high lower limit and a high upper limit. Further, in the case of keeping the Tni of the liquid crystal composition high and improving the temperature stability, it is preferable that the amount has a high lower limit and a high upper limit. In order to keep the driving voltage of the liquid crystal display element low, when the Δε of the liquid crystal composition is increased, it is preferable that the lower limit and the upper limit are low.

When reliability is important, R ^L1 and R ^L2 are each independently preferably an alkyl group, and when importance is attached to reducing the volatility of the compound, R ^L1 and R ^L2 are each independently. , An alkoxy group is preferable, and when importance is attached to reduction of viscosity, at least one of R ^L1 and R ^L2 is preferably an alkenyl group.
The number of halogen atoms present in the compound represented by the general formula (L) is preferably 0, 1, 2 or 3, and more preferably 0 or 1. Further, when importance is placed on compatibility with other liquid crystal molecules, the number of halogen atoms is preferably one.

When the ring structure to which they are bonded is a benzene ring (aromatic ring), R ^L1 and R ^L2 are each independently a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group. Is preferably an alkoxy group having 1 to 4 carbon atoms or an alkenyl group having 4 to 5 carbon atoms.
When the ring structure to which they are bonded is a saturated ring structure such as a cyclohexane ring, a pyran ring, or a dioxane ring, R ^L1 and R ^L2 are each independently a straight-chain carbon atom having 1 to 5 carbon atoms. An alkyl 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, R ^L1 and R ^L2 each independently preferably have a total of carbon atoms and oxygen atoms (when present) of 5 or less, and may be linear. preferable.

各式中の黒点は結合手を表す。 The alkenyl group is preferably a group selected from the group represented by the following formulas (R1) to (R5).

The black dots in each formula represent a bond.

n ^L1 is preferably 0 when importance is attached to the response speed of the liquid crystal molecules, 2 or 3 is preferable when improving the maximum temperature of the nematic phase of the liquid crystal molecules, and 1 is preferable when balancing these. Further, in order to satisfy the characteristics required for the liquid crystal composition, it is preferable to combine compounds having different values of n ^L1 .

A ^L1 , A ^L2 and A ^L3 are each independently preferably an aromatic group when increasing Δn of the liquid crystal molecule and an aliphatic group when improving the response speed of the liquid crystal molecule.
Examples of the aromatic group or aliphatic group include 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 the structure represented by the following chemical formula 72 is more preferable, A trans-1,4-cyclohexylene group or a 1,4-phenylene group is more preferable.

Ｚ^Ｌ１およびＺ^Ｌ２は、それぞれ独立して、液晶分子の応答速度を重視する場合は単結合が好ましい。

Z ^L1 and Z ^L2 are each independently preferably a single bond when importance is attached to the response speed of liquid crystal molecules.

The compound represented by the general formula (L) is preferably a compound represented by the following general formulas (L-1) to (L-7).
The compound represented by formula (L-1) is the following compound.

In the formula, R ^L11 and R ^L12 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
R ^L11 and R ^L12 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 carbon atom 2 to 2 An alkenyl group of 5 is preferred.

The compounds represented by general formula (L-1) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (L-1) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit 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 mass %, 35 mass %, 30 mass %, 25 mass %.

When keeping the viscosity (η) of the liquid crystal composition low and increasing the response speed, the amount of the compound represented by formula (L-1) preferably has a high lower limit and a high upper limit. Further, in the case where the Tni of the liquid crystal composition is kept high and the temperature stability is improved, it is preferable that the lower limit of the amount be moderate and the upper limit thereof be moderate. In order to keep the driving voltage of the liquid crystal display element low, when the Δε of the liquid crystal composition is increased, it is preferable that the lower limit and the upper limit are low.

式中、Ｒ^Ｌ１２は、一般式（Ｌ−１）における意味と同じ意味を表す。 The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-1).

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

The compound represented by the general formula (L-1-1) is preferably a compound represented by the following formulas (L-1-1.1) to (L-1-1.3), L-1-1.2) or a compound represented by formula (L-1-1.3) is more preferable, and a compound represented by formula (L-1-1.3) is preferable. More preferable.

The amount of the compound represented by 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.

式中、Ｒ^Ｌ１２は、一般式（Ｌ−１）における意味と同じ意味を表す。 The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-2).

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

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 values are 1% by mass, 5% by mass, 10% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 27% by mass, 30% by mass, 35% by mass. %. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 42% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass and 30% by mass.

The compound represented by the general formula (L-1-2) is preferably a compound represented by the following formulas (L-1-2.1) to (L-1-2.4), The compounds represented by L-1-2.2) to (L-1-2.4) are more preferred. In particular, the compound represented by the formula (L-1-2.2) is preferable because it has a high effect of improving the response speed of the liquid crystal composition.
In addition, in the case where improvement in Tni is required over the response speed of the liquid crystal composition, it is preferable to use the compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The amount of the compound represented by formula (L-1-2.3) or formula (L-1-2.4) contained in the liquid crystal composition is less than 30% by mass in order to increase the solubility at low temperature. Is preferred.

The compound represented by the general formula (L-1) is preferably a compound represented by the following 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 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 carbon number 2 to 2. An alkenyl group of 5 is preferred.

The amount of the compound represented by formula (L-1-3) 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, 20% by mass, 23% by mass, 25% by mass and 30% by mass. On the other hand, the preferable upper limit values are 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 mass %, 20 mass %, 17 mass %, 15 mass %, 13 mass %, and 10 mass %.

The compound represented by the general formula (L-1-3) has the following formulas (L-1-3.1) to (L-1-3.4) or formulas (L-1-3.11) to (L-1-3.11). L-1-3.13) is preferred, and the compound is represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4). It is more preferable that the compound is In particular, the compound represented by the formula (L-1-3.1) is preferable because it has a high effect of improving the response speed of the liquid crystal composition.
Further, in order to improve Tni higher than the response speed of the liquid crystal composition, the formula (L-1-3.3), the formula (L-1-3.4), and the formula (L-1-3.11). ) Or a compound represented by the formula (L-1-3.12) is preferably used. Formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) contained in the liquid crystal composition. The total amount of the compounds represented by is preferably less than 20% in order to increase the solubility at low temperatures.

The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-4) 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 carbon number 2 to 2. An alkenyl group of 5 is preferred.

The amount of the compound represented by 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.

The compound represented by the general formula (L-1-4) or (L-1-5) has the following formulas (L-1-4.1) to (L-1-4.3) or the formula (L- 1-5.1) to (L-1-5.3) are preferred compounds represented by the formula (L-1-4.2) or the formula (L-1-5.2). More preferably, the compound is

The compound represented by the general formula (L-1) has the formula (L-1-1.3), the formula (L-1-2.2), the formula (L-1-3.1) and the formula (L -1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12). It is preferable to combine the above, formula (L-1-1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3). It is more preferable to combine two or more selected from the compounds represented by formula (L-1-3.4) and formula (L-1-4.2).

When importance is placed on the reliability of the liquid crystal composition, the compounds represented by the formula (L-1-3.1), the formula (L-1-3.3) and the formula (L-1-3.4) are used. It is preferable to combine two or more selected from the compounds represented by formula (L-1-1.3) and formula (L-1-2.2) when the response speed of the liquid crystal composition is emphasized. It is preferable to combine two or more selected ones.

式中、Ｒ^Ｌ１７およびＲ^Ｌ１８は、それぞれ独立して、メチル基または水素原子を表す。 The compound represented by the general formula (L-1) is also preferably a compound represented by the following 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 values are 1% by mass, 5% by mass, 10% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 27% by mass, 30% by mass, 35% by mass. %. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 42% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass and 30% by mass.

The compound represented by the general formula (L-1-6) is preferably a compound represented by the following formulas (L-1-6.1) to (L-1-6.3).

式中、Ｒ^Ｌ２１およびＲ^Ｌ２２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ｒ^Ｌ２１は、炭素原子数１〜５のアルキル基または炭素原子数２〜５のアルケニル基が好ましい。
Ｒ^Ｌ２２は、炭素原子数１〜５のアルキル基、炭素原子数４〜５のアルケニル基または炭素原子数１〜４のアルコキシ基が好ましい。 The compound represented by formula (L-2) is the following compound.

In the formula, R ^L21 and R ^L22 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
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 compounds represented by formula (L-2) may be used alone or in combination of two or more. The type of compound to be combined 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.

The amount of the compound represented by formula (L-2) 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.

When the solubility of liquid crystal molecules at low temperature is important, a large amount of the compound represented by formula (L-2) is effective, and when the response speed of the liquid crystal composition is important, The effect is high when the amount is set to a small amount. Furthermore, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (L-2) to the middle of the above range.

The compound represented by the general formula (L-2) is preferably a compound represented by the following formulas (L-2.1) to (L-2.6), and the compound represented by the formula (L-2.1) More preferably, it is a compound represented by formula (L-2.3), formula (L-2.4) or formula (L-2.6).

式中、Ｒ^Ｌ３１およびＲ^Ｌ３２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ｒ^Ｌ３１およびＲ^Ｌ３２は、それぞれ独立して、炭素原子数１〜５のアルキル基、炭素原子数４〜５のアルケニル基、または炭素原子数１〜４のアルコキシ基が好ましい。 The compound represented by formula (L-3) is the following compound.

In the formula, R ^L31 and R ^L32 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
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 compounds represented by formula (L-3) may be used alone or in combination of two or more. The type of compound to be combined 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.

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.

In order to obtain a high birefringence, a large amount of the compound represented by the general formula (L-3) is effective, and when a high Tni is important, a small amount thereof is effective. Is high. Furthermore, in the case of improving the drop mark and the image sticking property, it is preferable to set the amount of the compound represented by the general formula (L-3) to the middle of the above range.

The compound represented by the general formula (L-3) is represented by the following formulas (L-3.1) to (L-3.4), formula (L-3.6) or formula (L-3.7). The compound represented by the formula (L-3.2) to (L-3.4), the compound represented by the formula (L-3.6) or the formula (L-3.7) is preferable. It is preferable to have.

式中、Ｒ^Ｌ４１およびＲ^Ｌ４２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ｒ^Ｌ４１は、炭素原子数１〜５のアルキル基または炭素原子数２〜５のアルケニル基が好ましい。
Ｒ^Ｌ４２は、炭素原子数１〜５のアルキル基、炭素原子数４〜５のアルケニル基または炭素原子数１〜４のアルコキシ基が好ましい。 The compound represented by formula (L-4) is the following compound.

In the formula, R ^L41 and R ^L42 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
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) may be used alone, or may be used in combination of two or more kinds. The type of compound to be combined 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.

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 preferable lower limit value 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, It is 30 mass %, 35 mass %, and 40 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 compound represented by the general formula (L-4) is preferably a compound represented by the following formulas (L-4.1) to (L-4.3).

Depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence, the liquid crystal composition may contain only the compound represented by formula (L-4.1), It may include only the compound represented by the formula (L-4.2), or both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2). Well, all of the compounds represented by formulas (L-4.1) to (L-4.3) may be included.

The compound represented by the general formula (L-4) is also preferably a compound represented by the following formulas (L-4.4) to (L-4.6), and the compound represented by the formula (L-4.4) The compound represented by is more preferable.

Depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence, the liquid crystal composition may contain only the compound represented by formula (L-4.4), It may include only the compound represented by the formula (L-4.5), and includes both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5). But it's okay.

The compound represented by the general formula (L-4) is also preferably a compound represented by the following formulas (L-4.7) to (L-4.10), and the compound represented by the formula (L-4.9) The compound represented by is more preferable.

式中、Ｒ^Ｌ５１およびＲ^Ｌ５２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ｒ^Ｌ５１は、炭素原子数１〜５のアルキル基または炭素原子数２〜５のアルケニル基が好ましい。
Ｒ^Ｌ５２は、炭素原子数１〜５のアルキル基、炭素原子数４〜５のアルケニル基、または炭素原子数１〜４のアルコキシ基が好ましい。 The compound represented by formula (L-5) is the following compound.

In the formula, R ^L51 and R ^L52 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
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 formula (L-5) may be used alone or in combination of two or more. The type of compound to be combined 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.

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.
The preferable lower limit value 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, It is 30 mass %, 35 mass %, and 40 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 compound represented by the general formula (L-5) is preferably a compound represented by the following formula (L-5.1) or formula (L-5.2), and preferably a compound represented by the formula (L-5.1). It is more preferable that the compound is

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

The compound represented by the general formula (L-5) is also preferably a compound represented by the following formulas (L-5.5) to (L-5.7), and the compound represented by the formula (L-5.7) is also preferred. The compound represented by is more preferable.

式中、Ｒ^Ｌ６１およびＲ^Ｌ６２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ｘ^Ｌ６１およびＸ^Ｌ６２は、それぞれ独立して、水素原子またはフッ素原子を表す。
Ｒ^Ｌ６１およびＲ^Ｌ６２は、それぞれ独立して、炭素原子数１〜５のアルキル基または炭素原子数２〜５のアルケニル基が好ましい。
Ｘ^Ｌ６１およびＸ^Ｌ６２のうちの一方がフッ素原子、他方が水素原子であることが好ましい。 The compound represented by formula (L-6) is the following compound.

In the formula, R ^L61 and R ^L62 have the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom.
R ^L61 and R ^L62 are each independently preferably 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 compounds represented by formula (L-6) may be used alone or in combination of two or more. The type of compound to be combined 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.

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 value 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.
It should be noted that, when focusing on increasing Δn, it is preferable to increase the amount of the compound represented by the general formula (L-6), and when focusing on precipitation at low temperature, the amount should be increased. It is preferable to reduce the amount.

The compound represented by the general formula (L-6) is preferably a compound represented by the following formulas (L-6.1) to (L-6.9).

The type of compound to be combined is not particularly limited, but it is preferable to use 1 to 3 types, and more preferably 1 to 4 types. In addition, the fact that the selected compound has a wide molecular weight distribution is also effective for solubility. Therefore, for example, one selected from the compounds represented by formula (L-6.1) and formula (L-6.2), and 1 from the compounds represented by (L-6.4) and formula (L-6.5) and 1 from the compounds represented by formula (L-6.6) and formula (L-6.7). It is preferable to select one kind and one kind from the compounds represented by the formula (L-6.8) and the formula (L-6.9), and to combine these appropriately. Among them, they are represented by formula (L-6.1), formula (L-6.3), formula (L-6.4), formula (L-6.6) and formula (L-6.9). A combination of compounds is more preferable.

The compound represented by the general formula (L-6) is also preferably a compound represented by the following formulas (L-6.10) to (L-6.17), and the compound represented by the formula (L-6.11) is also preferred. The compound represented by is more preferable.

式中、Ｒ^Ｌ７１およびＲ^Ｌ７２は、それぞれ一般式（Ｌ）におけるＲ^Ｌ１およびＲ^Ｌ２と同じ意味を表す。
Ａ^Ｌ７１およびＡ^Ｌ７２は、それぞれ一般式（Ｌ）におけるＡ^Ｌ２およびＡ^Ｌ３と同じ意味を表す。ただし、Ａ^Ｌ７１およびＡ^Ｌ７２中に存在する任意の水素原子は、フッ素原子で置換されてもよい。
Ｚ^Ｌ７１は、一般式（Ｌ）におけるＺ^Ｌ２と同じ意味を表す。
Ｘ^Ｌ７１およびＸ^Ｌ７２は、それぞれ独立して、フッ素原子または水素原子を表す。 The compound represented by formula (L-7) is the following compound.

In the formula, R ^L71 and R ^L72 represent the same meanings as R ^L1 and R ^L2 in the general formula (L), respectively.
A ^L71 and A ^L72 have the same meanings as A ^L2 and A ^L3 in the general formula (L), respectively. However, any hydrogen atom present in A ^L71 and A ^L72 may be replaced by a fluorine atom.
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 each independently preferably 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. However, any hydrogen atom present in A ^L71 and A ^L72 may be replaced by a fluorine atom.
Z ^L71 is preferably a single bond or COO-, more preferably a single bond.
Each of X ^L71 and X ^L72 is preferably a hydrogen atom.

The type of compound to be combined 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, and four types.
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.

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 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.
When a high Tni of the liquid crystal composition is required, it is preferable to increase the amount of the compound represented by the general formula (L-7), and when low viscosity is desired, decrease the amount. Is preferred.

The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.1) to (L-7.4), and the compound represented by the formula (L-7.2) The compound represented by is more preferable.

The compound represented by the general formula (L-7) is also preferably a compound represented by the following formulas (L-7.11) to (L-7.13), and the compound represented by the formula (L-7.11) is also preferred. The compound represented by is more preferable.

The compound represented by the general formula (L-7) is also preferably a compound represented by the following formulas (L-7.21) to (L-7.23), and the compound represented by the formula (L-7.21) is also preferred. The compound represented by is more preferable.

The compound represented by the general formula (L-7) is also preferably a compound represented by the following formulas (L-7.31) to (L-7.34), and the compound represented by the formula (L-7.31) is also preferred. Alternatively, the compound represented by the formula (L-7.32) is more preferable.

The compound represented by the general formula (L-7) is also preferably a compound represented by the following formulas (L-7.41) to (L-7.44), and the compound represented by the formula (L-7. 41) or a compound represented by the formula (L-7.42) is more preferable.

Further, the compound represented by the general formula (L-7) is also preferably a compound represented by the following formulas (L-7.51) to (L-7.53).

((Polymerizable compound))
The liquid crystal composition may further contain a polymerizable compound that can be polymerized by irradiation with active energy rays. The polymerizable compound is preferably a compound represented by the following general formula (P). Further, the liquid crystal composition preferably contains one kind or two or more kinds of such a polymerizable compound.

In the formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or —Sp ^p2 —P ^p2 . However, one or two or more non-adjacent -CH2- in the alkyl group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or It may be substituted with -OCO-. In addition, one or more hydrogen atoms in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.

P ^p1 and P ^p2 each independently represent one of the following general formulas (P ^p1-1 ) to formula (P ^p1-9 ).

(In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W ^p11 is a single bond, Represents an —O—, —COO— or methylene group, and t ^p11 represents 0, 1 or 2, but when a plurality of R ^p11 , R ^p12 , W ^p11 and/or t ^p11 are present in the molecule, they are It may be the same or different.)

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group.
Z ^p1 and Z ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, _{-COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S ^{-, - CH = CR ZP1 -COO} -, - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - ^{COO-CR ZP1 = CH-OCO} -, - OCO-CR ZP1 = CH-COO -, - OCO-CR ZP1 = CH-OCO -, - (CH 2) z -COO -, - (CH 2) 2 -OCO _{-, - OCO- (CH 2)} 2 -, - (C = O) -O- (CH 2) 2 -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF _{-, - CF 2 -, -} CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡C- ^{(wherein, R ZP1} Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when a plurality of R ^ZP1's are present in the molecule, they may be the same or different. ..

A ^p1 , A ^p2 and A ^p3 are each independently,
(A ^p )1,4-cyclohexylene group (one or two or more non-adjacent —CH ₂ — present in this group may be substituted with —O—).
^(B p) 1,4-phenylene group (one present in the group or not adjacent two or more -CH = may be replaced by -N =.) And ^(c p) naphthalene-2,6 ,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene-2,6- Diyl group (one or two or more non-adjacent -CH= present in these groups may be replaced by -N=, and a hydrogen atom present in this group is a halogen atom or a carbon atom number 1). May be substituted by an alkyl group having 8 to 8 or an alkenyl group having 1 to 8 carbon atoms.)
Represents a group selected from the group consisting of the group ^(a p), group ^{(b p)} and group ^{(c p)} are each independently an alkyl group having 1 to 8 carbon atoms, 1 to carbon atoms 8 may be substituted with an alkenyl group, a cyano group, a fluorine atom, a chlorine atom or -Sp ^p2- P ^p2 .

m ^p1 represents 0, 1, 2 or 3.
When there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^{p2 in the} molecule, they may be the same or different. However, A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or anthracene-2,6-diyl group.
However, the alignment aid is excluded from the polymerizable compound.

R ^p1 is preferably —Sp ^p2 —P ^p2 .
It is preferable that P ^p1 and P ^p2 are each independently one of the formulas (P ^p1 -1) to (P ^p1 -3), and more preferably (P ^p1 -1).
R ^p11 and R ^p12 are preferably each independently a hydrogen atom or a methyl group.
^tp11 is preferably 0 or 1.
W ^p11 is preferably a single bond, a methylene group or an ethylene group.
m ^p1 is preferably 0, 1 or 2, and is preferably 0 or 1.

Z ^p1 and ^{Z p2} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 _{-, - OCOC 2 H 4 -} , - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) 2 -COO _{-, - (CH 2) 2} -OCO -, - OCO- (CH 2) 2 -, - CH = CH-COO -, - COO-CH = CH -, - OCOCH = CH -, - COO- (CH 2 ) ₂ -, - OCF ₂ - or a is preferably -C≡C-, a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - _{COOC 2 H 4 -, - OCOC} 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) _{2 -OCO -, - OCO- (CH} 2) 2 -, - CH = CH-COO -, - COO-CH = CH -, - OCOCH = CH -, - COO- (CH 2) 2 - or -C≡ It is more preferably C-.

Only one of Z ^p1 and Z ^p2 existing in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC ₂ H ₄ —, _{-OCOC 2 H 4 -, - C} 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - _{OCO- (CH 2) 2 -,} - CH = CH-COO -, - COO-CH = CH -, - OCOCH = CH -, - COO- (CH 2) 2 - or a -C≡C-, other Are all single bonds, and only one of Z ^p1 and Z ^p2 present in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO— or —OCO. It is more preferable that all of them are a single bond, and it is further preferable that all of Z ^p1 and Z ^p2 existing in the molecule are single bonds.
Further, only one of Z ^p1 and Z ^p2 existing in the molecule is —CH═CH—COO—, —COO—CH═CH—, —(CH ₂ ) ₂ —COO—, —(CH ₂ ) _{2 -OCO -, - O-CO- (} CH 2) 2 -, - COO- (CH 2) 2 - is a linking group selected from the group consisting of, it is preferable others are all single bonds.

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group, and the spacer group is preferably an alkylene group having 1 to 30 carbon atoms. However, -CH ₂ in the alkylene group - is, -O insofar as each other oxygen atoms are not linked directly -, - CO -, - COO -, - OCO -, - substituted with CH = CH- or -C≡C- The hydrogen atom in the alkylene group may be replaced with a halogen atom.
Among them, Sp ^p1 and Sp ^p2 are preferably each independently a linear alkylene group having 1 to 10 carbon atoms or a single bond.

A ^p1 , A ^p2 and A ^p3 are each independently preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, and more preferably a 1,4-phenylene group.
The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with liquid crystal molecules (liquid crystal compounds).

The total content of the compounds represented by formula (P) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, based on the liquid crystal composition. , 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, further preferably 0.2 to 2% by mass, and 0.2 to 1.3% by mass. The content is more preferably mass%, particularly preferably 0.2 to 1 mass%, and most preferably 0.2 to 0.56 mass%.

A preferable lower limit value of the total content of the compounds represented by the general formula (P) is 0.01% by mass, 0.03% by mass, and 0.05% by mass with respect to the liquid crystal composition. Yes, 0.08% by mass, 0.1% by mass, 0.15% by mass, 0.2% by mass, 0.25% by mass, 0.3% by mass.
The preferable upper limit of the total content of the compounds represented by formula (P) is 10% by mass, 8% by mass, 5% by mass, and 3% by mass with respect to the liquid crystal composition. Yes, 1.5% by mass, 1.2% by mass, 1% by mass, 0.8% by mass, and 0.5% by mass.

When the content of the compound represented by the general formula (P) is low, the effect of adding this compound to the liquid crystal composition is unlikely to be exhibited, and the alignment regulating force of the liquid crystal molecule may be reduced depending on the kind of the liquid crystal molecule or the alignment aid. Problems such as weakness or weakening over time may occur. On the other hand, when the content of the compound represented by the general formula (P) is too large, the amount of such a compound remaining after curing becomes large, or the curing takes time, depending on the illuminance of active energy rays, for example, and the liquid crystal composition. There may be a problem that the reliability of the product decreases, and a problem of storage stability as a solution such as precipitation occurs. Therefore, it is preferable to set the content in consideration of these balances.

The total content of the compound represented by the general formula (SAL) (that is, the alignment aid which is a compound containing the adsorption group Z ^AT1 ) and the compound represented by the general formula (P) is based on the liquid crystal composition. It is preferably 0.05 to 10% by mass, preferably 0.1 to 8% by mass, preferably 0.1 to 5% by mass, and 0.1 to 3% by mass. Preferably, it is 0.2 to 2% by mass, preferably 0.2 to 1.3% by mass, preferably 0.2 to 1% by mass, and 0.2 to 0% by mass. It is preferably 0.56% by mass.

A preferable lower limit value of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 0.01% by mass relative to the liquid crystal composition, and the preferable lower limit value is 0. 03% by mass, 0.05% by mass, 0.08% by mass, 0.1% by mass, 0.15% by mass, 0.2% by mass, 0.25% by mass %, and 0.3% by mass.
The preferable upper limit of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 10% by mass, and 8% by mass with respect to the liquid crystal composition. Yes, 5 wt%, 3 wt%, 1.5 wt%, 1.2 wt%, 1 wt%, 0.8 wt%, 0.5 wt% is there.

When the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is small, the effect of adding these compounds to the liquid crystal composition is difficult to appear, and for example, the type of liquid crystal molecules Depending on the circumstances, there may be a problem that the alignment regulating force of the liquid crystal molecules is weak or weakened with time. On the other hand, if the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is too large, the compound may remain after curing depending on, for example, the illuminance of active energy rays. In some cases, problems such as an increase in the amount to be applied, a long time for curing, and a decrease in reliability of the liquid crystal composition may occur. For this reason, it is preferable to set their contents in consideration of these balances.

Preferable examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).

式中、Ｐ^ｐ１１、Ｐ^ｐ１２、Ｓｐ^ｐ１１及びＳｐ^ｐ１２は、一般式（Ｐ）におけるＰ^{ｐ １}、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 have the same meanings as P ^{p 1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

式中、Ｐ^ｐ２１、Ｐ^ｐ２２、Ｓｐ^ｐ２１及びＳｐ^ｐ２２は、一般式（Ｐ）におけるＰ^{ｐ １}、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。 Moreover, as a preferable example of the compound represented by General formula (P), the polymeric compound represented by following formula (P-2-1)-formula (P-2-12) is also mentioned.

In the formula, P ^p21 , P ^p22 , Sp ^p21, and Sp ^p22 have the same meanings as P ^{p 1} , P ^p2 , Sp ^p1, and Sp ^p2 in the general formula (P).

Furthermore, as a preferable example of the compound represented by the general formula (P), a polymerizable compound represented by the following formula (P-3-1) to formula (P-3-15) can also be mentioned.

式中、Ｐ^ｐ３１、Ｐ^ｐ３２、Ｓｐ^ｐ３１及びＳｐ^ｐ３２は、一般式（Ｐ）におけるＰ^{ｐ １}、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

In the formula, P ^p31 , P ^p32 , Sp ^p31, and Sp ^p32 have the same meanings as P ^{p 1} , P ^p2 , Sp ^p1, and Sp ^p2 in the general formula (P).

Moreover, as a preferable example of the compound represented by General formula (P), the polymeric compound represented by following formula (P-4-1)-formula (P-4-15) is also mentioned.

式中、Ｐ^ｐ４１、Ｐ^ｐ４２、Ｓｐ^ｐ４１及びＳｐ^ｐ４２は、一般式（Ｐ）におけるＰ^{ｐ １}、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 have the same meanings as P ^{p 1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

When the liquid crystal composition further contains a polymerizable compound in addition to the alignment aid, the pretilt angle of liquid crystal molecules can be formed appropriately. Such a polymerizable compound is a pretilt angle forming aid having a function of forming a pretilt angle of liquid crystal molecules.
The liquid crystal composition 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 importance is placed on the reliability and long-term stability of the liquid crystal composition, the amount of the compound having a carbonyl group contained in the liquid crystal composition is preferably 5% by mass or less, and more preferably 3% by mass or less. More preferably, it is still more preferably 1 mass% or less, and particularly preferably substantially 0 mass %.
Further, when importance is attached to the stability of the liquid crystal composition by UV irradiation, the amount of the compound in which a chlorine atom is substituted in the liquid crystal composition is preferably 15% by mass or less, and 10% by mass or less. More preferably, it is more preferably 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and substantially 0% by mass. Particularly preferred.

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, it is preferably 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 95 mass% or more, and particularly preferably substantially 100 mass %.
In order to suppress deterioration of the liquid crystal composition due to oxidation, it is preferable to reduce the amount of the compound having a cyclohexenylene group as a ring structure contained in the liquid crystal composition, specifically, 10% by mass or less. Is preferable, it is preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably substantially 0% by mass. ..

When the improvement of the viscosity of the liquid crystal composition and the improvement of Tni are emphasized, a liquid crystal composition of a compound having in its molecule a 2-methylbenzene-1,4-diyl group in which a hydrogen atom may be replaced by a halogen is included. It is preferable to reduce the amount contained, specifically, it is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, and 3% by mass. The following is particularly preferable, and it is most preferable that the content be substantially 0% by mass.
Here, in the present specification, "the amount of the compound X contained in the liquid crystal composition is substantially 0% by mass" means that the compound X unintentionally (unavoidably) mixed into the liquid crystal composition. It means that the amount of

The preferred lower limit of the average elastic constant (K _AVG ) of the liquid crystal composition 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, respectively.
When it is important to reduce the power consumption of the liquid crystal display element, it is effective to suppress the light amount of the backlight, and it is preferable to improve the light transmittance of the liquid crystal display element. Therefore, the value of K _AVG is set to be low. It is preferable. When emphasis is placed on improving the response speed of the liquid crystal display element (liquid crystal composition), it is preferable to set the value of K _AVG to a high value.

In the present embodiment, the polymerizable monomer contains both the alignment aid and the pretilt angle forming aid (polymerizable compound) described above, but in the present invention, the polymerizable monomer is the alignment aid and the pretilt. Only one of the horn-forming aids may be included.

(Liquid crystal display element)
Next, a liquid crystal display device including a liquid crystal layer formed of the above liquid crystal composition will be described.
1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element, and FIG. 2 is an enlarged plan view of a region surrounded by I line in FIG.
Note that, in FIGS. 1 and 2, for convenience, dimensions and ratios thereof are exaggerated and may be different from actual ones. In addition, the materials, dimensions, and the like shown below are examples, and the present invention is not limited to these, and can be appropriately modified 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, 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 region surrounded by these forms a unit pixel of the liquid crystal display element 1. One pixel electrode 13 is formed in each unit pixel.

The pixel electrode 13 has a structure (so-called fishbone structure) including two trunks that are orthogonal to each other and have a cross shape, and a plurality of branches that branch from each trunk and extend outward. There is.
A Cs electrode 14 is provided between the pair of gate bus lines 11 in parallel with 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 More preferably, it is formed of 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, AZTO (AlZnSnO).
The average thickness of the transparent electrode is preferably about 10 to 200 nm. Further, in order to reduce 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 stripe-shaped 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 onto the second substrate 3 in a predetermined pattern, and then heated or irradiated with light to be cured. The color filter 9 can be obtained by performing this operation for three colors of red, green, and blue.
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 can also be configured 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.
A spacer may be arranged between the active matrix substrate AM and the color filter substrate CF to keep the distance between them. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacer columns formed by a photolithography method.
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 contrast by adjusting the positional relationship of their transmission axes. Specifically, it is preferable that the first polarizing plate 7 and the second polarizing plate 8 are arranged so that their transmission axes are orthogonal to each other so that they 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 so that its transmission axis 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.

The active matrix substrate AM is an organic insulation that further covers a part of the pixel electrode layer 5 (gate bus line 11, data bus line 12, pixel electrode 13, Cs electrode 14 and thin film transistor) or the entire pixel electrode layer 5. A membrane may be included.
Further, the color filter substrate CF may further include an organic insulating film that covers a part of the common electrode layer 6 (common electrode) or the entire common electrode layer 6.
Examples of the constituent material of the organic insulating film include acrylic resin, epoxy resin, styrene resin, and copolymers thereof. These resins may be used alone or in combination of two or more.

In the present embodiment, each of the active matrix substrate AM and the color filter substrate CF includes a polymerized product of a polymerizable monomer, and the presence of the polymerized product causes a surface in contact with the liquid crystal layer 4 (hereinafter, “substrate AM, CF”). The surface roughness (Ra) of the "contact surface" is a predetermined value.
The polymer of the polymerizable monomer may form a film on the inner surface of the pixel electrode layer 5 or the common electrode layer 6, or may form a plurality of island-shaped spots.
In the former case, the contact surface between the substrates AM and CF is the surface of the film made of the polymer (the surface opposite to the pixel electrode layer 5 or the common electrode layer 6). On the other hand, in the latter case, the contact surface between the substrates AM and CF is a surface composed of the inner surface exposed from the spot of the pixel electrode layer 5 or the common electrode layer 6 and the surface of the spot.

Here, the surface roughness (Ra) affects the vertical alignment of liquid crystal molecules. If the surface roughness (Ra) is too small, sufficient vertical alignment of liquid crystal molecules cannot be obtained, so that the surface roughness (Ra) has a lower limit value. On the other hand, in order to improve the vertical alignment of the liquid crystal molecules, it is preferable that the surface roughness (Ra) is large to some extent.
However, according to the study by the present inventors, when the surface roughness (Ra) is too large, the alignment of liquid crystal molecules is disturbed due to the unevenness present on the contact surface of the substrates AM and CF, and the scattering thereby causes the liquid crystal display element. It was found that the contrast of the image displayed in No. 1 decreased. Therefore, there is an upper limit value for the surface roughness (Ra).

The inventors of the present invention have conducted further studies to set the surface roughness (Ra) to 1 to 30 nm, whereby the liquid crystal display element 1 capable of displaying an image having high contrast while sufficiently aligning the liquid crystal molecules vertically. The present invention has been completed and the present invention has been completed.
The surface roughness (Ra) may be 1 to 30 nm, but is preferably 1 to 20 nm, more preferably 1 to 10 nm. By setting the surface roughness (Ra) in such a range, the above effect can be further improved.
The surface roughness (Ra) is an arithmetic average roughness defined in JIS B 0601:2003.

(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 according to the present embodiment includes a preparatory step [1] for preparing a substrate and a liquid crystal composition, a hydrophilic treatment step [2] for subjecting the substrate to a hydrophilic treatment, and an assembly for assembling the liquid crystal display element 1. The method has a step [3], a polymerization step [4] for polymerizing the orientation aid and/or the polymerizable compound, and a curing step [5] 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] Hydrophilization treatment step (first step)
Next, the surfaces of the active matrix substrate AM and the color filter substrate CF that come into contact with the liquid crystal layer 4 (contact surfaces of the substrates AM and CF) are subjected to a hydrophilic treatment. Note that this step may be performed as necessary and may be omitted.
By performing the hydrophilic treatment, the hydrophilicity of the contact surface between the substrates AM and CF (hereinafter, also simply referred to as “contact surface”) can be increased. Therefore, the polar group of the alignment aid contained in the liquid crystal composition can be firmly fixed to the inner surface. In addition, the alignment aid can be oriented so that the mesogenic group is separated from the contact surface. As a result, the surface roughness (Ra) of the contact surface can be easily set within the above range, and the liquid crystal molecules in the liquid crystal layer 4 can be more reliably held in a vertically aligned state.

Examples of the hydrophilic treatment (polarity improving treatment) include physical treatment such as ozone treatment, corona treatment, and oxygen plasma treatment, addition of a surfactant, polyethylene glycol, polyvinyl alcohol, etc., introduction of a functional group having hydrophilicity. The chemical treatments such as These treatments can be used alone or in combination of two or more.
Among them, the hydrophilic treatment is preferably a physical treatment, more preferably an ozone treatment. According to the ozone treatment, it is possible to introduce a hydroxyl group into the contact surface to enhance hydrophilicity (polarity). Further, since the ozone treatment (physical treatment) has a high cleaning effect, it is possible to remove impurities (eg, resist residue) attached to the inner surface. Therefore, the polar group of the alignment aid is more easily adsorbed on the contact surface.

<Ozone treatment>
Ozone treatment is a method in which oxygen in the air is converted to ozone by ultraviolet (UV) irradiation and surface modification is performed in an ozone-containing atmosphere.
A low-pressure mercury lamp is preferable as the UV light source. The low-pressure mercury lamp has an emission spectrum at wavelengths near 185 nm and 254 nm, produces ozone with light having a wavelength near 185 nm, and decomposes ozone with light having a wavelength near 254 nm to produce active oxygen. Is known to do. Therefore, by using the low-pressure mercury lamp, the contact surface can be efficiently hydrophilized.

The ozone source gas may be any gas containing oxygen, and may be oxygen gas, dry air, or the like.
Further, the pressure of the atmosphere for the ozone treatment may be either reduced pressure or atmospheric pressure.
The time of ozone treatment (UV irradiation time) is not particularly limited, but is preferably about 10 to 100 seconds, more preferably about 20 to 60 seconds.
<Corona treatment>
The corona treatment is a method of performing surface modification using corona discharge excited by applying a high-voltage alternating current to a pair of electrodes under atmospheric pressure.

<Oxygen plasma treatment>
Oxygen plasma treatment is a method in which a treatment gas containing oxygen gas is ionized by arc discharge and oxygen plasma generated at this time is used to perform surface modification.
As the processing gas, a mixed gas of oxygen gas and an inert gas such as nitrogen gas, argon gas or helium gas can be used.
The supply amount of oxygen gas is preferably about 0.5 to 50 sccm, and the pressure of the atmosphere is preferably about 0.1 to 50 Pa.
The power applied from the power supply during arc discharge is preferably about 10 to 500 W, and the frequency of the power supply is preferably about 1 to 50 kHz.

The static contact angle of water at 25° C. is preferably 70° or less, and more preferably 60° or less in the entire area of the contact surface after the hydrophilic treatment.
When the pixel electrode layer 5 and the common electrode layer 9 include an organic insulating film, the static contact angle of water on the surface of the organic insulating film at 25° C. is preferably 70° or less, and is about 40 to 55°. Is more preferable. The static contact angle of water on the surface of the ITO film (metal oxide film) at 25° C. is preferably 30° or less, and more preferably about 10 to 20°.

In addition, the surface free energy is preferably 50 mN/m or more, and more preferably 60 mN/m or more in the entire area of the contact surface after the hydrophilic treatment.
When the pixel electrode layer 5 and the common electrode layer 9 include an organic insulating film, the surface free energy of the surface of the organic insulating film is preferably 50 mN/m or more, more preferably about 55 to 65 mN/m. .. The surface free energy of the surface of the ITO film (metal oxide film) is preferably 70 mN/m or more, more preferably about 75 to 85 mN/m.

By setting the static contact angle and the surface free energy within the above ranges, the alignment aid can be uniformly supplied to almost the entire contact surface, and the alignment aid is more strongly adsorbed (fixed) on the contact surface. can do.

[3] Assembly process (second process)
Next, the sealing 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.
Then, under a reduced pressure, a predetermined amount of the liquid crystal composition is dropped inside the sealing material, and then the active matrix substrate AM and the color filter substrate CF are arranged to face each other so as to come into contact with the liquid crystal composition.
In such a drop injection (ODF: One Drop Fill) method, it is necessary to drop 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 pressure change or impact in the dropping device that occurs at the time of dropping, and it is possible to continue dropping stably for a long time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

Particularly in a small-sized liquid crystal display element that is often used in smartphones, it is difficult to control the deviation amount within a certain range because the optimum injection amount of the liquid crystal composition is small. 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 device.
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.

[4] Polymerization step (third step)
When the alignment aid contains a polymerizable group and/or when the liquid crystal composition contains a polymerizable compound, the liquid crystal composition is irradiated with an active energy ray such as an ultraviolet ray or an electron beam to thereby align the alignment aid. The agent and/or the polymerizable compound are polymerized.
Thereby, the liquid crystal layer 4 is formed, and the liquid crystal display element 1 is obtained. At this time, since the alignment aid is fixed on the two substrates AM and CF, the alignment aid and/or the polymerized compound of the polymerizable compound is unevenly distributed in the liquid crystal layer 4 toward the substrates AM and CF.
In order to obtain good alignment of 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 are opposed to each other so as to contact the liquid crystal composition as in this embodiment, at least the substrate located on the irradiation surface side is suitable for the active energy rays. It must have good transparency.
Further, the polymerization may be carried out in multiple steps as follows. Specifically, first, only the alignment aid and/or the polymerizable compound present in a specific region of the liquid crystal composition is polymerized using a mask. Then, conditions such as an electric field, a magnetic field, or temperature are adjusted to change the alignment state of liquid crystal molecules in the unpolymerized region. In this state, the active energy ray is further irradiated to polymerize the alignment aid and/or the polymerizable compound existing in the unpolymerized region.

Particularly, when ultraviolet rays are used, it is preferable to apply 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, and more preferably about 60 Hz to 10 kHz.
The alternating 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 AC voltage.
In the horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle to 80 to 89.9° from the viewpoint of alignment stability and contrast.
The applied voltage (electric field) may be direct current depending on the type of liquid crystal display element 1 to be manufactured, the degree of pretilt angle to be formed, and the like.

The temperature at which the ultraviolet rays are irradiated 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.
A metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or the like can be used as the lamp that generates ultraviolet rays.
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.

At this time, for example, by appropriately adjusting the irradiation time of the active energy ray for irradiation, the amount of the alignment aid contained in the liquid crystal composition, and the like, the surface roughness (Ra) caused by the polymer of the polymerizable monomer can be determined. It can be set within the above range.
The intensity of the active energy ray (in particular, ultraviolet ray) for irradiation 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 . The active energy ray may be irradiated while changing the intensity.
The energy amount of the active energy ray (in particular, ultraviolet ray) to be irradiated can be appropriately adjusted, but is preferably about 10 mJ/cm ^{2 to} 500 J/cm ² , and is about 100 mJ/cm ^{2 to} 200 J/cm ^2. Is more preferable.

Further, the time for irradiating the active energy ray (especially ultraviolet ray) is appropriately selected depending on its intensity, but is preferably about 10 to 7200 seconds, more preferably about 10 to 3600 seconds, and 10 to 600 seconds. More preferably, it is about second.
On the other hand, the amount of the alignment aid contained in the liquid crystal composition is preferably about 0.1 to 3% by mass, more preferably about 0.2 to 1.5% by mass, and 0.3 to 1% by mass. % Is more preferable.

In the liquid crystal composition as described above, since the alignment aid does not inhibit the polymerization reaction of the polymerizable compound, the polymerizable compounds are preferably polymerized with each other, and the unreacted polymerizable compound remains in the liquid crystal composition. Can be suppressed.
In addition, in the [3] assembling process, a vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, the seal material is screen-printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF so that the injection port remains. After that, the two substrates AM and CF are bonded together, and the sealing material is thermoset by heating. Next, after sealing the injection port, the process proceeds to [4] 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 display element and the method for manufacturing the liquid crystal display element of the present invention have been described above, the present invention is not limited to the above-described embodiments.
For example, in the liquid crystal display element of the present invention, a part of the configuration may be replaced with another configuration that exhibits the same function, or an arbitrary configuration may be added. Further, the method for manufacturing a liquid crystal display element of the present invention may have an additional step having an arbitrary purpose, and may be replaced with an arbitrary step that can obtain the same action and effect.
In addition, in the liquid crystal display element of the above-described embodiment, both the active matrix substrate AM and the color filter substrate CF are in direct contact with the liquid crystal layer 4 without interposing the polyimide (PI) alignment film, but only one of them is provided. A PI alignment film may be provided. In this case, the surface of the PI alignment film may or may not be hydrophilized. Further, in this case, the surface roughness (Ra) of the surface of the PI alignment film may not be in the above range.
Further, considering the influence of heat when forming the PI alignment film, the color filter substrate CF is preferable if the PI alignment film is provided. In other words, when the hydrophilic treatment is applied to only one of the substrates, the active matrix substrate AM (the substrate having the pixel electrode 13) is preferable.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
A liquid crystal mixture was prepared by mixing 10 kinds of liquid crystal molecules as described above. The properties of the obtained liquid crystal mixture were as follows.
Nematic phase-isotropic liquid phase transition temperature (Tni): 75°C
Refractive index anisotropy (Δn) at 293 K: 0.112
Dielectric anisotropy (Δε) at 293K: -3.0
Rotational viscosity at 293K (γ1): 122 mPa·s
Elastic constant of spread at 293K (K11): 14.1 pN
Elastic constant of bending at 293K (K33): 13.9 pN

1. Preparation of sample (Sample No. 1)
First, a first substrate provided with an ITO film, an ITO film, and a second substrate provided with an organic insulating film made of acrylic resin (manufactured by JSR, “Optomer SS”) formed on the ITO film are provided. I prepared.
Next, the sealing material was drawn in a closed loop bank shape along the edge of the first substrate using a dispenser.
Then, under normal pressure, a predetermined amount of the liquid crystal composition was dropped into the frame drawn with the sealing material, and the first substrate and the second substrate were opposed to each other in a depressurized state so as to come into contact with the liquid crystal composition. After that, the first substrate and the second substrate were bonded together. Here, in order to temporarily cure the sealing material, a mask is applied to a portion corresponding to the liquid crystal composition, and only a portion of the sealing material is exposed to ultraviolet rays having a wavelength of 365 nm and an illuminance of 4.0 mW/cm ² by using a high pressure mercury lamp. Was irradiated.

Sample No. In No. 1, a liquid crystal composition containing a liquid crystal mixture and a pretilt angle forming auxiliary (polymerizable compound) as a polymerizable monomer was used. The amount of the pretilt angle forming aid contained in the liquid crystal composition was 0.3% by mass.
Then, while applying a rectangular alternating current wave of 10 V and 100 Hz, ultraviolet rays having a wavelength of 365 nm and an illuminance of 100 m/cm ² were irradiated for 50 seconds using a high pressure mercury lamp. Furthermore, in order to fully cure the sealing material, it was annealed at 120° C. for 1 hour and left at room temperature to obtain a liquid crystal cell for evaluation.
Next, a liquid crystal cell was sandwiched between a pair of polarizing plates arranged so that their transmission axes were orthogonal to each other, to obtain a sample.

(Sample No. 2)
The sample No. was changed except that the type of liquid crystal composition was changed. A sample was prepared in the same manner as in 1.
Sample No. In No. 2, a liquid crystal composition containing the liquid crystal mixture and the alignment aid 1 and the pretilt angle forming aid as the polymerizable monomer was used. The amount of the alignment aid 1 contained in the liquid crystal composition was 0.3% by mass, and the amount of the polymerizable compound was 0.3% by mass.

(Sample No. 3)
The sample No. 1 was changed except that the amount of the alignment aid 1 contained in the liquid crystal composition was changed to 0.5% by mass. A sample was prepared in the same manner as in 2.
(Sample No. 4)
The sample No. 1 except that the amount of the alignment aid 1 contained in the liquid crystal composition was changed to 1.0% by mass. A sample was prepared in the same manner as in 2.

(Sample No. 5)
The sample No. was changed except that the type of liquid crystal composition was changed. A sample was prepared in the same manner as in 1.
Sample No. In No. 5, the liquid crystal composition containing the liquid crystal mixture and the alignment aid 1, the alignment aid 2, and the pretilt angle forming aid as the polymerizable monomer was used. The amount of the alignment aid 1 contained in the liquid crystal composition was 1.0% by mass, the amount of the alignment aid 2 was 0.6% by mass, and the amount of the pretilt angle forming aid was 0.3% by mass. ..

(Sample Nos. 6 to 10)
The sample No. was changed except that the irradiation time of ultraviolet rays was changed to 100 seconds. Samples were prepared in the same manner as 1-5.
(Sample Nos. 11 to 15)
The sample No. was changed except that the irradiation time of ultraviolet rays was changed to 200 seconds. Samples were prepared in the same manner as 1-5.
Each sample was prepared in duplicate.

2. Measurement and evaluation 2-1. Measurement of Surface Roughness (Ra) Each sample was disassembled to measure the surface roughness (Ra) of the surface of the ITO film and the surface of the organic insulating film.
The surface roughness (Ra) was measured with an atomic force microscope (Pacific Nanotechnology, "Nano-DST") using a close contact mode (measurement mode) and a cantilever (Nanoworld, "NCH-W"). It was

2-2. Evaluation of Vertical Alignment Light was transmitted through each sample, and the degree of light transmission (luminance unevenness) was evaluated according to the following three-stage criteria.
<Evaluation criteria>
◯: Almost the entire surface of the sample is displayed in black.
Δ: Only the vicinity of the sample where the liquid crystal composition was dropped is displayed in black.
X: Almost the entire surface of the sample is not displayed in black.

2-3. Measurement of Pretilt Angle For each sample, the pretilt angle was measured using a pretilt angle measurement system (“PSA-301 type” manufactured by Toyo Technica).

2-4. Evaluation of Response Characteristics With respect to each sample, the response speed at 20° C. was measured by an electro-optical measuring device (“DMS703” manufactured by Autotronic Co., Ltd.), and the response characteristics were evaluated according to the following criteria.
<Evaluation criteria>
◎: Less than 9.0 ms ◯: 9.0 ms or more, less than 10.0 ms △: 10.0 ms or more, less than 11.0 ms ×: 11.0 ms or more

2-5. Evaluation of Contrast With respect to each sample, electro-optical characteristics were measured by an electro-optical measuring device (“DMS703” manufactured by AUTORONIC), and “maximum luminance/minimum luminance” was calculated. The contrast was evaluated according to the following criteria based on the calculated values.
<Evaluation criteria>
◎: 1600 or more ◯: 1400 or more and less than 1600 △: 1200 or more and less than 1400 ×: less than 1200

The results of these measurements and evaluations are shown in Table 1.

In addition, various compounds were used as the alignment aid 1 and the alignment aid 2, and the above measurement and evaluation were performed. It was confirmed that the surface roughness of the ITO film and the organic insulating film changed depending on the difference in the contained amount and/or the irradiation time of ultraviolet rays. Further, the difference in the value of the surface roughness due to the difference in the types of the alignment aid 1 and the alignment aid 2 was not so large.

(Sample Nos. H-1 to H-4)
The sample No. was changed except that each component was used and the amount used was changed as shown in Table 2. In the same manner as in No. 1, sample No. Samples H-1 to H-4 were prepared.
Further, the same measurement and evaluation as described above were performed for each of the obtained samples. The results of these measurements and evaluations are also shown in Table 2.

From the comparison between Table 1 and Table 2, sample No. 1 to 15 (Examples) are sample No. It was confirmed that the performance was superior to that of H-1 to H-4 (Comparative example).

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 (10)

A liquid crystal display device comprising a liquid crystal layer containing liquid crystal molecules sandwiched between two substrates,
Of the two substrates, one substrate is a substrate that directly contacts the liquid crystal layer without an alignment film,
The one substrate is present in contact with the liquid crystal layer, and comprises a polymer of a single or a plurality of polymerizable monomers polymerizable by irradiation with an active energy ray,
The polymerizable monomer has a function of spontaneously aligning the liquid crystal molecules, and includes an alignment aid having a polar group, and a pretilt angle forming aid having a function of forming a pretilt angle of the liquid crystal molecules. ,
The polar group includes one or more groups selected from the group consisting of an oxygen-containing cyclic group, a nitrogen-containing cyclic group, an oxygen-containing chain group and a nitrogen-containing chain group itself or the group,
The oxygen-containing cyclic group is any of the following groups,

(In the formula,
* Represents a bond. )
The nitrogen-containing cyclic group is any of the following groups,

(In the formula,
* Represents a bond. )
The oxygen-containing chain group is any of the following groups,

(In the formula,
* Represents a bond,
R ^at1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
Z ^at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and in the alkylene group or alkenylene group is, -O so that oxygen atoms are not directly adjacent - - -CH ₂ of, - COO -, - C ( = O) -, - OCO- may be substituted with,
X ^at1 is an alkyl group having a carbon number of 1 to 15, -CH ₂ in the alkyl group - is, as the oxygen atoms are not directly adjacent -O -, - COO -, - C (= O) - , -OCO- may be substituted. )
The nitrogen-containing chain group is any of the following groups,

(In the formula,
* Represents a bond,
R ^at , R ^bt , R ^ct and R ^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )
The alignment aid is a polymerizable group for polymerizing, a mesogenic group similar to liquid crystal molecules, the polar group capable of interacting with a member in direct contact with the liquid crystal layer, and an alignment inducer for inducing alignment of the liquid crystal molecules. Has a group and
The polymer forms a plurality of island-shaped spots on the surface of the one substrate in contact with the liquid crystal layer,
The liquid crystal display element, wherein the one substrate has a surface roughness (Ra) of 1 to 30 nm on a surface in contact with the liquid crystal layer due to the presence of the polymer. The liquid crystal display element according to claim 1 , wherein the one substrate is a substrate including a pixel electrode. The other of the two substrates also includes the polymer that is present in contact with the liquid crystal layer, and the presence of the polymer causes the surface roughness (Ra) of the surface in contact with the liquid crystal layer to be 1 The liquid crystal display element according to claim 1 or 2 , having a thickness of -30 nm. The liquid crystal display element according to claim 3 , wherein the other substrate is a substrate that directly contacts the liquid crystal layer without an alignment film. The other substrate, the liquid crystal display device according to claim 3 or 4 which is a substrate provided with a color filter. The liquid crystal molecules, the liquid crystal display device according to any one of claims 1 to 5 whose dielectric anisotropy is negative. The liquid crystal display device, PSA type, PSVA type, VA type, IPS type liquid crystal display device according to any one of claims 1 6 are FFS type or ECB type. A method of manufacturing a liquid crystal display device according to any one of claims 1 to 7,
A step of disposing the two substrates so as to face each other so as to come into contact with a liquid crystal composition containing the liquid crystal molecules and the polymerizable monomer;
A step of polymerizing the polymerizable monomer by irradiating the active energy ray while applying a voltage to the liquid crystal composition to obtain the polymer. Method. The polymerizable monomer includes an alignment aid having a function of spontaneously aligning the liquid crystal molecules,
The method for producing a liquid crystal display device according to claim 8 , wherein the total amount of the alignment aid contained in the liquid crystal composition is 0.1 to 3 mass %. The irradiation time of the active energy rays, a method of manufacturing a liquid crystal display device according to claim 8 or 9, which is 10 to 7200 seconds.

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