JPWO2019069697A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

A monovalent organic group having a group represented by Ki1 in cyclophane (Ki1 represents a substituent represented by the following formulas (K-1) to (K-16)) and R1 ( R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or Pi1-Spi1-, wherein -CH2- in the alkyl group is -CH = CH-,- C≡C—, —O—, —NH—, —CO—, —COO— or —OCO—, but —O— is not continuous. The above object is achieved by a liquid crystal composition containing two or more kinds and a liquid crystal display device containing the same.

Description

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

  Conventionally, in a VA liquid crystal display, a polyimide alignment film (PI) layer is provided on an electrode to induce vertical alignment of liquid crystal molecules when no voltage is applied and to achieve horizontal alignment of liquid crystal molecules when a voltage is applied. Yes. However, since a large amount of cost is required for forming the PI layer, in recent years, methods for realizing the alignment of liquid crystal molecules have been studied while omitting the PI layer.

  For example, Patent Document 1 discloses a liquid crystal medium based on a mixture of polar compounds having negative dielectric anisotropy and containing at least one spontaneous alignment additive. It is described as being highly suitable for use in displays that do not contain any alignment layer. And in patent document 1, the specific compound which has a hydroxyl group is used as a spontaneous orientation additive.

Special table 2014-524951 gazette

  However, according to the study by the present inventors, when the self-alignment additive described in Patent Document 1 is used, the alignment regulating force to align liquid crystal molecules vertically is not sufficient, and the spontaneous alignment It has been found that there is room for improvement in terms of the storage stability of the liquid crystal composition containing the additive.

  Accordingly, an object of the present invention is to provide a spontaneous alignment aid for a liquid crystal composition that can ensure storage stability when added to a liquid crystal composition and enables vertical alignment of liquid crystal molecules without providing a PI layer. is there. Another object of the present invention is to use the liquid crystal composition containing the spontaneous alignment additive, which has excellent storage stability and allows vertical alignment of liquid crystal molecules without providing a PI layer, and the liquid crystal composition. The object is to provide a liquid crystal display element.

The present invention provides a monovalent organic group having a group represented by K ⁱ¹ in cyclophane (K ⁱ¹ represents a substituent represented by the following general formula (K-1) to general formula (K-16)). And R ¹ (R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or P ⁱ¹ —Sp ⁱ¹ —, and — CH ₂ — may be substituted with —CH═CH—, —C≡C—, —O—, —NH—, —CO—, —COO— or —OCO—, but —O— Provided is a liquid crystal composition containing one or two or more of the compounds substituted).

(Where
W ^K1 represents a methine group, C—CH ₃ , C—C ₂ H _5, C—C ₃ H _7, C—C ₄ H ₉ or a nitrogen atom,
W ^K2 represents a single bond, —CH ₂ —, an oxygen atom or a sulfur atom,
X ^K1 and Y ^K1 each independently represent —CH ₂ —, an oxygen atom or a sulfur atom,
Z ^K1 represents an oxygen atom or a sulfur atom,
U ^K1 , V ^K1 and S ^K1 each independently represent a methine group or a nitrogen atom, except for the combination of [U ^K1 is a methine group, V ^K1 is a methine group, and S ^K1 is a nitrogen atom]. In (K-1) to general formula (K-16), the black dot at the left end represents a bond. )
The present invention also provides a liquid crystal display device using the liquid crystal composition.

  According to the present invention, a liquid crystal composition containing the spontaneous alignment additive having excellent storage stability and capable of uniform vertical alignment of liquid crystal molecules without providing a PI layer, and a liquid crystal display using the liquid crystal composition An element can be provided.

It is a figure which shows typically one Embodiment of a liquid crystal display element. FIG. 2 is an enlarged plan view of a region surrounded by an I line in FIG. 1.

(Spontaneous alignment aid for liquid crystal composition)
The liquid crystal composition of this embodiment is a monovalent organic group having a group represented by K ⁱ¹ in cyclophane as a spontaneous alignment aid for the liquid crystal composition (K ⁱ¹ is represented by the following general formula (K-1) to And R ¹ (R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or P. ⁱ¹ —Sp ⁱ¹ — represents —CH ₂ — in the alkyl group is —CH═CH—, —C≡C—, —O—, —NH—, —CO—, —COO— or —OCO—. It may be substituted, but -O- is not continuous) contains one or more compounds substituted.

(Where
W ^K1 represents a methine group, C—CH ₃ , C—C ₂ H _5, C—C ₃ H _7, C—C ₄ H ₉ or a nitrogen atom,
W ^K2 represents a single bond, —CH ₂ —, an oxygen atom or a sulfur atom,
X ^K1 and Y ^K1 each independently represent —CH ₂ —, an oxygen atom or a sulfur atom,
Z ^K1 represents an oxygen atom or a sulfur atom,
U ^K1 , V ^K1 and S ^K1 each independently represent a methine group or a nitrogen atom, except for the combination of [U ^K1 is a methine group, V ^K1 is a methine group, and S ^K1 is a nitrogen atom]. In (K-1) to general formula (K-16), the black dot at the left end represents a bond. )
The spontaneous alignment aid for a liquid crystal composition of the present embodiment has a structure in which a monovalent organic group having a group represented by K ⁱ¹ is substituted on cyclophane, and as K ⁱ¹ , formula (K-1) to Since it contains a compound having a structure represented by any one of formulas (K-16), when used in a liquid crystal composition, it is adsorbed on a substrate sandwiching the liquid crystal composition (liquid crystal layer), and the liquid crystal The molecules can be held in a vertically oriented state. Therefore, according to the spontaneous alignment aid for a liquid crystal composition of the present embodiment, liquid crystal molecules are aligned without providing a PI layer (inducing vertical alignment of liquid crystal molecules when no voltage is applied and horizontal alignment of liquid crystal molecules when voltage is applied). Orientation). As described above, a compound in which a monovalent organic group having a group represented by K ⁱ¹ is substituted on cyclophane is preferably used for assisting spontaneous alignment of liquid crystal molecules in a liquid crystal composition. In the group represented by K ⁱ¹ , only one cyclophane may be substituted, or a plurality of groups may be substituted. In the group represented by K ⁱ¹ , it is preferable that an organic group bonded to cyclophane forms the major axis direction of the compound and is bonded to the terminal of the organic group. If having a plurality of groups represented by K ^i1, groups represented by a plurality of K ⁱ¹ is preferably located on one side of the end of the long axis of the compound.

In addition, the inventors of the present invention have a structure in which the spontaneous alignment aid for a liquid crystal composition of the present embodiment has a structure in which a monovalent organic group having a group represented by ^Ki1 is substituted on a cyclophane. It has been found that not only the molecular orientation but also the storage stability of the liquid crystal composition can be secured.
If importance is placed on chemical stability as spontaneous orientation ^aid, the ^{K i1 (K-1),} (K-3), (K-8), (K-9), (K-10) ( K-11), (K-12), (K-14), (K-15), and (K-16) are preferable, and when importance is attached to the orientation of the liquid crystal, (K-1) to (K -7), (K-10), (K-11), (K-12), (K-14), (K-15) and (K-16) are preferred, and the solubility in liquid crystal compounds is important. When viewing, (K-1), (K-8), (K-10), (K-15) and (K-16) are preferred, and when these balances are important, (K- 1), (K-3), (K-9), (K-11), (K-12), (K-15) and (K-16) are more preferred.

From the above viewpoint, the compound contained in the spontaneous alignment aid for a liquid crystal composition of the present embodiment has an organic group bonded to cyclophane, preferably at the terminal of the main chain of the organic group bonded to cyclophane, only to have a group represented by K ^i1, the chemical structure of the merged group represented by K ^i1, and cyclophane structure is not particularly limited as long as it does not inhibit the function of the liquid crystal composition .

The compound in which a monovalent organic group having a group represented by K ⁱ¹ is substituted on cyclophane preferably has one or two or more alkylene groups having 3 or more carbon atoms in the compound. In the alkylene group, one or two or more non-adjacent —CH ₂ — may be substituted with —O—, —CO—, —COO—, —OCO— or —C (═CH ₂ ) —. Good. When the group having an alkylene group having 3 or more carbon atoms is bonded to cyclophane, the orientation of the liquid crystal composition can be improved.

The compound monovalent organic group having a group represented by ^{K i1} to cyclophane is substituted, preferably, one or more ^{P i1 -Sp} i1 - ^(P i1 has the following general Represents a group selected from the group represented by formula (P-1) to general formula (P-16) (in the formula, the black dot at the right end represents a bond);

Sp ⁱ¹ represents an alkylene group having 1 to 20 carbon atoms or a direct bond, and one or two or more non-adjacent —CH ₂ — in the alkylene group is substituted with —O—, —COO— or —OCO—. May be. )
It is preferable to have. P ⁱ¹ -Sp ⁱ¹ - By having a pretilt angle of the liquid crystal molecules can be suitably formed.

  The cyclophane compound has the general formula (i):

(Wherein X and Y each independently represent an oxygen atom, a carbonyl group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a single bond, one in the alkylene group or two or more not adjacent to each other) —CH ₂ — may be substituted with —O—, —CO—, —COO—, —OCO— or —C (═CH ₂ ) —, and the hydrogen atom in the alkylene group is substituted with the substituent L ( L may be substituted with R ⁱ¹ , R ⁱ² and R ⁱ³ ), but —O— is not continuous,
Z ⁱ¹ and Z ⁱ² are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO—, —CF _{2 O -, - OCF 2 -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - _{OCOC (CH 3) = CH -} , - CH 2 -CH (CH 3) COO -, - OCOCH (CH 3) -CH 2 -, - OCH 2 CH 2 O-, or an alkylene group having 2 to 20 carbon atoms In the alkylene group, one or two or more non-adjacent —CH ₂ — may be substituted with —O—, —COO— or —OCO—, and A ⁱ¹ and A ⁱ² are each independently Divalent 6-membered aromatic group, Divalent 6-membered ring heterocycle Kozokumoto, divalent 6-membered ring aliphatic group, a divalent 6-membered heterocyclic aliphatic group, a hydrogen atom is a substituent L (L of these ring structure, R ^i1, R ⁱ² and R ^It represents the same meaning as ⁱ³ .), but when there are a plurality of Z ⁱ¹ , Z ⁱ² , Z ⁱ² and A ⁱ² , they may be the same or different from each other,
And R ^{i1, R i2} and ^{R i3} is independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl ^group, a group represented by ^{K i1 (K i1} Represents a group selected from the group represented by formulas (K-1) to (K-16)) or P ⁱ¹ -Sp ⁱ¹ — (P ⁱ¹ represents a polymerizable group, and Sp ⁱ¹ represents a spacer group or The secondary carbon atom in the alkyl group is substituted with —CH═CH—, —C≡C—, —O—, —NH—, —COO— or —OCO—. -O- is not continuous,
m ⁱ¹ and m ⁱ² represent an integer of 0 to 5;
n contains 1 type, or 2 or more types of the compound represented by the integer of 1-10. )
It is preferable that it is a compound represented by these.
The compound represented by the general formula (i) contained in the spontaneous alignment aid for a liquid crystal composition of the present embodiment is, for example, the general formula (i-1) or the general formula (i-2).

(Wherein X, Y, A ⁱ¹ , A ⁱ² , Z ⁱ¹ , Z ⁱ² , R ⁱ¹ , R ⁱ² , R ⁱ³ , m ⁱ¹ , m ⁱ² and n are each independently X in the general formula (i) Y, A ⁱ¹ , A ⁱ² , Z ⁱ¹ , Z ⁱ² , R ⁱ¹ , R ⁱ² , R ⁱ³ , m ⁱ¹ , m ^i2, and n have the same meaning.)
(Hereinafter also referred to as “compound (i-1)” and “compound (i-2)”).

In formula (i), formula (i-1) and formula (i-2), Z ⁱ¹ and Z ⁱ² are preferably a single bond, —CH═CH—, —C≡C—, —COO—, — OCO -, - OCOO -, - OOCO -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO- _{, -OCOC (CH 3) = CH} -, - CH 2 -CH (CH 3) COO -, - OCOCH (CH 3) -CH 2 -, - OCH 2 CH 2 O-, or 1 to 40 carbon atoms A linear or branched alkylene group, or a group in which one or two or more non-adjacent —CH ₂ — in the alkylene group is substituted with —O—, more preferably a single bond, —COO -, -OCO-, -CH = CHCOO-, -OCOCH = CH-,- _{CH 2 -CH 2 COO -, -} OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3) = CH -, - CH 2 -CH (CH 3) COO -, - OCOCH (CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—, a linear or branched alkylene group having 1 to 40 carbon atoms, or one or not two or more adjacent in the alkylene group —CH ₂ — is —O—, a single bond, a linear alkylene group having 2 to 15 carbon atoms, or one or two or more non-adjacent —CH ₂ — in the alkylene group is —O. - represents been substituted with, more preferably, single _{bond, CH 2 -CH 2 COO -,} - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3) = _{CH -, - CH 2 -CH (} CH 3) COO-, _{OCOCH (CH 3) -CH 2 -} , - OCH 2 CH 2 O-, or an alkylene group (ethylene group _(-CH 2 _CH 2 -)) of the carbon atoms 2 or -CH ₂ in the ethylene group - one Is a group substituted with —O— (—CH ₂ O—, —OCH ₂ —), a linear alkylene group having 3 to 13 carbon atoms, or one or two or more non-adjacent ones in the alkylene group Represents a group in which —CH ₂ — is substituted with —O—.

A ⁱ¹ and A ⁱ² preferably represent a divalent 6-membered aromatic group or a divalent 6-membered aliphatic group, but are divalent unsubstituted 6-membered aromatic groups, divalent non-valent A substituted 6-membered cycloaliphatic group or a hydrogen atom in these ring structures is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. A divalent unsubstituted 6-membered aromatic group, a group in which a hydrogen atom in the ring structure is substituted with a fluorine atom, or a divalent unsubstituted 6-membered aliphatic group is preferred. A hydrogen atom on the substituent is preferably a 1,4-phenylene group, a 2,6-naphthalene group or a 1,4-cyclohexyl group, which may be substituted by a halogen atom, an alkyl group or an alkoxy group, but at least one One of the substituents is ^P i1 ^{-Sp i1} - substituted with There. Specific examples of the divalent 6-membered aromatic group or the divalent 6-membered aliphatic group include a 1,4-phenylene group, a 1,4-cyclohexylene group, an anthracene-2,6-diyl group, Phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, cyclopentane-1,3-diyl group, indane-2, It preferably represents a ring structure selected from a 5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and a 1,3-dioxane-2,5-diyl group.

X and Y preferably represent an oxygen atom, a linear or branched alkylene group having 1 to 20 carbon atoms or a single bond, and one or two or more non-adjacent —CH ₂ — in the alkylene group. Is preferably substituted with —O—, —COO—, —OCO—, —COO—C (═CH ₂ ) — or —OCO—C (═CH ₂ ) —, and a hydrogen atom in the alkylene group preferably substituted with - the ^{K i1} or ^P i1 ^{-Sp i1.} More specifically, X and Y are preferably structures represented by the following formula (ia).

(In the formula, p represents an integer of 1 to 20, q represents 0 or 1, is bonded to the benzene ring constituting the cyclophane with * at the left end, and A ⁱ¹ , A ⁱ² , R ⁱ¹ or It binds to any of R ⁱ² , wherein —CH ₂ — is —O—, —COO—, —OCO—, —COO—C (═CH ₂ ) — or —OCO—C (═CH ₂ ) —. And a hydrogen atom in the formula may be substituted with K ⁱ¹ or P ⁱ¹ -Sp ⁱ¹ —.) A plurality of X and Y in the general formula (i) are the same. It may or may not be.

R ^{i1, R i2,} and ^{R i3} is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogenated alkyl ^{group, K i1} or ^P i1 ^{-Sp i1} - may represent preferably an alkyl The secondary carbon atom in the group is preferably substituted with -O-, -OCO-, or -COO- (however, -O- is not continuous), more preferably a hydrogen atom, Represents a linear or branched alkyl group having 1 to 18 carbon atoms, K ⁱ¹ or P ⁱ¹ —Sp ⁱ¹ —, and the secondary carbon atom in the alkyl group is —O—, —OCO— (however, —O -Is not continuous).

One of R ⁱ¹ or ^{R i2} is ^{K i1} or ^P i1 ^{-Sp i1} - preferably represents a. R ⁱ³ preferably represents a hydrogen atom. A plurality of R ⁱ¹ , R ⁱ² and R ⁱ³ may be the same or different. For example, all of n R ⁱ¹ in the general formula (i) may be the same group, or R ⁱ¹ may represent different groups such as K ⁱ¹ and P ⁱ¹ -Sp ⁱ¹ —. Similarly, the n R ⁱ² and R ⁱ³ in the general formula (i) may all be the same group or different.

m ⁱ¹ and m ⁱ² preferably represent an integer of 0 to 3, more preferably an integer of 0 to 1.

When m ⁱ¹ and m ⁱ² represent 0, it is preferable that —X—R ⁱ¹ and —Y—R ⁱ² have a structure represented by the following formula ( ^ia -1).

(In the formula, p represents an integer of 1 to 20, q represents 0 or 1, m represents an integer of 1 to 4, and R ^ia1 independently represents a hydrogen atom, K ⁱ¹ or P ⁱ¹ -Sp ^i1. In the formula, —CH ₂ — represents —O—, —COO—, —OCO—, or —C (═CH ₂ ) —. The hydrogen atom in the formula may be substituted with K ⁱ¹ or P ⁱ¹ -Sp ⁱ¹ —.
In the formula (i-a-1), a hydrogen atom in the formula ^P i1 ^{-Sp i1} - When substituted ^{by, R ia1} is ^{K i1} or ^P i1 ^{-Sp i1} - preferably represents a. More specifically, the following formula (ia-11) or formula (ia-12) is preferable.

( ^Wherein p ¹ represents an integer of ¹ to 10, m represents an integer of 1 to 4, R ^ia11 independently represents K ⁱ¹ or P ⁱ¹ -Sp ⁱ¹ —, and cyclophane is represented by * at the left end. It is combined with the benzene ring that constitutes
A preferred combination of —X—R ⁱ¹ and —Y—R ⁱ² bonded to the same ring forming the cyclophane structure represents a group in which —X—R ⁱ¹ has K ⁱ¹ and / or P ⁱ¹ —Sp ⁱ¹ —. , -YR ⁱ² is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group. n is preferably an integer of 2 to 10, preferably an integer of 2 to 8, preferably an integer of 4 to 8, and preferably an integer of 4 to 6.

The compound represented by the general formula (i), the general formula (i-1), or the general formula (i-2) is a monovalent compound having one or more groups represented by K ⁱ¹ in the compound. has an organic group, if importance is placed on chemical stability as spontaneous orientation ^aid, the ^{K i1 (K-1),} (K-3), (K-8), (K-9), (K-10), (K-11), (K-12), (K-14), (K-15) and (K-16) are preferred, and when the orientation of the liquid crystal is important, K-1) to (K-7), (K-10), (K-11), (K-12), (K-14), (K-15) and (K-16) are preferred, and liquid crystal When importance is attached to the solubility in a compound, (K-1), (K-8), (K-10), (K-15) and (K-16) are preferred, and these balances are important. (K-1), ( -3), (K-9), (K-11), (K-12), more preferably (K-15) and (K-16).

In Formula (K-1) to Formula (K-16), W ^K1 preferably represents a single bond, a methine group, C—CH _3, or C—C ₄ H ₉ . X ^K1 and Y ^K1 each independently preferably represent —CH ₂ — or an oxygen atom. Z ^K1 preferably represents an oxygen atom.

Preferably, at least one selected from R ⁱ¹ , R ⁱ² , and R ⁱ³ preferably represents K ⁱ¹ , and at least one selected from R ⁱ¹ and R ⁱ² preferably represents K ⁱ¹ . Moreover, when X represents an alkylene group, it is preferable that the hydrogen atom in this alkylene group is substituted by ^Ki1 . If the monovalent organic group having a group represented by K ⁱ¹ there are multiple, linked backbone of a plurality of organic groups having a group represented by K ⁱ¹ respect cyclophane is in parallel in the same direction It is preferable.

Formula (i), the compound represented by the general formula (i1) or the general formula (i-2) is one or more ^P i1 ^{-Sp i1} - preferably has. Sp ⁱ¹ preferably represents a linear alkylene group or a single bond having 1 to 18 carbon atoms, more preferably represents a linear alkylene group or a single bond having 2 to 15 carbon atoms, and more preferably a carbon atom. A linear alkylene group or a single bond of formula 3 to 12 is represented.

^Preferably, R ^{i1, R i2,} and at least one or more ^P i1 ^{-Sp i1} selected from ^{R i3} - preferably representing ^the, or at least one selected from ^{R i1} and ^{R i2} are ^P i1 ^{-Sp i1} -Is preferably represented. If the monovalent organic group having a group represented by the presence of a plurality, ^P i1 ^{-Sp i1} respect cyclophane - - P ⁱ¹ -Sp ⁱ¹ is the main chain of a plurality of organic groups having a group represented by It is preferable that they are coupled in parallel in the same direction.

The group represented by K ⁱ¹ and P ⁱ¹ -Sp ^i1- are preferably present by substitution of the same ring forming the cyclophane structure. For example, it is preferable that R ⁱ¹ represents a group represented by K ⁱ¹ , R ⁱ² represents P ⁱ¹ -Sp ⁱ¹ —, and a monovalent organic group having a group represented by K ⁱ¹ further represents P ^i1. -sp ⁱ¹ - it is also preferable to have a. In addition, it is also preferable that the group represented by K ⁱ¹ and P ⁱ¹ -Sp ^i1- are present in different rings forming a cyclophane structure. In this case, the direction of the main chain of the organic group having a group represented by K ⁱ¹ and the organic group having P ⁱ¹ —Sp ⁱ¹ — can be appropriately selected with respect to cyclophane, but bonded in parallel in the same direction. It is preferable. More specifically, ^{R i1} or ^{R i2} presence of a plurality of the general formula (i) is ^{K i1} and ^P i1 ^{-Sp i1} independently - preferably represents a.

The compound represented by the general formula (i), the general formula (i-1) or the general formula (i-2) preferably has one or two or more alkylene groups having 3 or more carbon atoms, One or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO—. When there are a plurality of groups having an alkylene group having 3 or more carbon atoms, the main chain of the organic group having an alkylene group having 3 or more carbon atoms may be bonded in parallel to the cyclophane in the same direction. preferable. A monovalent organic group having a group represented by K ⁱ¹ and an organic group having an alkylene group having 3 or more carbon atoms are present by substitution of the same ring forming a cyclophane structure. It is preferable. In this case, it is preferable that a group represented by K ⁱ¹ is bonded to the terminal of the organic group having an alkylene group having 3 or more carbon atoms. In addition, it is also preferable that the monovalent organic group having a group represented by K ⁱ¹ and the organic group having an alkylene group having 3 or more carbon atoms exist as different organic groups, and the group represented by K ⁱ¹ The direction of the main chain of the organic group having π and the organic group having P ⁱ¹ -Sp ^i1- can be selected as appropriate, but it is preferable that they are bonded in parallel in the same direction.

  The cyclophane compound has the following general formula (ii) having no polymerizable group in the compound:

(Wherein X and Y each independently represent an oxygen atom, a carbonyl group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a single bond, one in the alkylene group or two or more not adjacent to each other) —CH ₂ — may be substituted with —O—, —CO—, —COO—, —OCO— or —C (═CH ₂ ) —, and the hydrogen atom in the alkylene group is substituted with the substituent L ( L represents the same meaning as R ⁱⁱ¹ , R ⁱⁱ² and R ⁱⁱ³ ).
Z ⁱⁱ¹ and Z ⁱⁱ² are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO—, —CF _{2 O -, - OCF 2 -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - _{OCOC (CH 3) = CH -} , - CH 2 -CH (CH 3) COO -, - OCOCH (CH 3) -CH 2 -, - OCH 2 CH 2 O-, or an alkylene group having 2 to 20 carbon atoms In the alkylene group, one or two or more non-adjacent —CH ₂ — may be substituted with —O—, —COO— or —OCO—, and A ⁱⁱ¹ and A ⁱⁱ² are each independently Divalent 6-membered aromatic group, Divalent 6 Heterocyclic aromatic group, a divalent 6-membered ring aliphatic group, a divalent 6-membered heterocyclic aliphatic group, these are the hydrogen atom of the ring structure substituent ^{L (L, R ii1, R} ii2 And R ⁱⁱ³ represent the same meaning)), but when there are a plurality of Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱ² and A ⁱⁱ² , they may be the same or different from each other. ,
R ⁱⁱ¹ , R ⁱⁱ² and R ⁱⁱ³ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or a group represented by K ^i1. The secondary carbon atom in the alkyl group may be substituted with —CH═CH—, —C≡C—, —O—, —NH—, —COO— or —OCO—, but —O— is continuous. Not to
m ⁱⁱ¹ and m ⁱⁱ² represent an integer of 0 to 5;
n contains 1 type, or 2 or more types of the compound represented by the integer of 1-10. )
It is also preferable that it is a compound represented by these.

In general formula (ii), preferred groups of X, Y, n, Z ⁱⁱ¹ , Z ⁱⁱ² , A ⁱⁱ¹ , A ⁱⁱ² , R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , m ⁱⁱ¹ and m ⁱⁱ² are in general formula (i). X, Y, n, Z ⁱ¹ , Z ⁱ² , A ⁱ¹ , A ⁱ² , R ⁱ¹ , R ⁱ² , R ⁱ³ , m ⁱ¹ and m ⁱ² represent the same meanings respectively.

More specific examples of general formula (i) and general formula (ii) include compounds represented by any of the following formulas (R-1-1) to (R-1-45). In the formula, R ⁱ¹ represents the same meaning as R ⁱ¹ in formula (i).

  Moreover, as a more specific example of general formula (i), the compound represented by either of following formula (P-1-1) to (P-1-44) is mentioned.

(Liquid crystal composition)
The liquid crystal composition of this embodiment contains one or more compounds in which a monovalent organic group having a group represented by K ⁱ¹ is substituted on the cyclophane. This liquid crystal composition has negative dielectric anisotropy (Δε).

The content of the cyclophane substituted with a monovalent organic group having a group represented by K ⁱ¹ is preferably 0.01 to 50% by mass, but the lower limit is more suitable for liquid crystal molecules. From the viewpoint of being aligned, the total amount of the liquid crystal composition is preferably 0.01% by mass, 0.1% by mass or more, 0.5% by mass or more, 0.7% by mass or more, or 1% by mass or more. It is. The upper limit of the content of compound (i) is preferably 50% by mass or less, 30% by mass or less, 10% by mass or less, and 7% by mass based on the total amount of the liquid crystal composition from the viewpoint of excellent response characteristics. Below, it is 5 mass% or less, 4 mass% or less, or 3 mass% or less.

  The liquid crystal composition has the general formulas (N-1), (N-2) and (N-3):

You may further contain the compound chosen from the compound group represented by either.

In formulas (N-1), (N-2) and (N-3),
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, and one or two or more adjacent ones in the alkyl group Each of —CH ₂ — may be independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be substituted with —N═),
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be substituted with —N═. ), And (d) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the groups (a), (b), (c) and (d) are independent of each other. May be substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH _2. O—, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—. Represent,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or an oxygen atom,
^nN11 , ^nN12 , ^nN21 , ^nN22 , ^nN31 and ^nN32 each independently represent an integer of 0 to 3, but ^nN11 + ^nN12 , ^nN21 + ^nN22 and ^nN31 + ^nN32 are each independent. 1, 2 or 3,
When a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 are present, each may be the same as or different from each other.

  The compound represented by any one of the general formulas (N-1), (N-2) and (N-3) is preferably a compound having a negative Δε and an absolute value larger than 3.

In the general formulas (N-1), (N-2), and (N-3), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31, and R ^N32 each independently represent 1 to 8 carbon atoms. An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and the number of carbon atoms An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable. More preferably, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

  Further, when the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

  The alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5) (the black dots in each formula represent a bond).

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, fat A trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5 -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 , 4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Preferred, the following structure:

Is more preferable, and a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group, or a 1,4-phenylene group is more preferable.

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

^XN21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, n ^A combination in which ^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 n 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 preferable.

  The lower limit of the preferable content of the compound represented by the formula (N-1) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 10% by mass or more, and 20% by mass or more. 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more Yes, 75 mass% or more, 80 mass% or more. The upper limit of the preferable content is 95% by mass or less, 85% by mass or less, 75% by mass or less, 65% by mass or less, 55% by mass or less, and 45% by mass or less, It is 35 mass% or less, 25 mass% or less, and 20 mass% or less.

  The lower limit of the preferable content of the compound represented by the formula (N-2) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 10% by mass or more, and 20% by mass or more. 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more Yes, 75 mass% or more, 80 mass% or more. The upper limit of the preferable content is 95% by mass or less, 85% by mass or less, 75% by mass or less, 65% by mass or less, 55% by mass or less, and 45% by mass or less, It is 35 mass% or less, 25 mass% or less, and 20 mass% or less.

  The lower limit of the preferable content of the compound represented by the formula (N-3) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 10% by mass or more, and 20% by mass or more. 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more Yes, 75 mass% or more, 80 mass% or more. The upper limit of the preferable content is 95% by mass or less, 85% by mass or less, 75% by mass or less, 65% by mass or less, 55% by mass or less, and 45% by mass or less, It is 35 mass% or less, 25 mass% or less, and 20 mass% or less.

  When a composition having a low response speed and a high response speed is required, the lower limit value is preferably low and the upper limit value is preferably low. Furthermore, when a composition having a high temperature stability and a high temperature stability is required, the lower limit value is preferably low and the upper limit value is preferably low. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is increased and the upper limit value is high.

  As a compound represented by general formula (N-1), the compound group represented by the following general formula (N-1a)-(N-1g) can be mentioned.

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na11} represents 0 or ^{1, n NB11} represents 0 or ^{1, n NC11} is represents 0 or ^{1, n Nd11} represents 0 or ^{1, n NE11} is 1 or ^{2, n Nf11} is 1 or ^{2, n NG11} is 1 or ^{2, a NE11} is trans-1,4 ^{-Represents a} cyclohexylene group or a 1,4-phenylene group, and ^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 ^{Ne 11} represents a single bond or ethylene, but at least one represents ethylene.)
More specifically, the compound represented by General Formula (N-1) is a compound selected from the group of compounds represented by General Formulas (N-1-1) to (N-1-21). Is preferred.

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

(In the formula, R ^N111 and R ^N112 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group, a pentyl group or a vinyl group. ^RN112 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 preferably an ethoxy group or a butoxy group.

  Although the compound represented by general formula (N-1-1) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-1) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15% by weight or more, 17% by weight or more, 20% by weight or more, 23% by weight or more, 25% by weight or more, 27% by weight or more, 30% by weight It is above, it is 33 mass% or more, and is 35 mass% or more. The upper limit of the preferable content is 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, and 33% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass Or less, 13 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, 3 mass% or less It is.

  Furthermore, the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.23). It is preferable that it is a compound represented by Formula (N-1-1.1) to (N-1-1.4), and Formula (N-1-1.1) and Formula (N The compound represented by -1-1.3) is preferable.

  The compounds represented by the formulas (N-1-1.1) to (N-1-1.22) can be used alone or in combination, but the composition of the present embodiment The lower limit of the preferred content of these compounds alone or with respect to the total amount of is 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, and 17% by mass 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, 35% by mass or more It is. The upper limit of the preferable content is 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, and 33% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass Or less, 13 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, 3 mass% or less It is.

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

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group. ^RN122 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 preferable. preferable.

  Although the compound represented by general formula (N-1-2) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-2) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 7% by mass or more, and 10% by mass. % Or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass These are 30% by mass or more, 33% by mass or more, 35% by mass or more, 37% by mass or more, 40% by mass or more, and 42% by mass or more. The upper limit of the preferable content is 50% by mass or less, 48% by mass or less, 45% by mass or less, 43% by mass or less, and 40% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass Or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, 8% by mass or less, and 7% by mass or less. It is 6 mass% or less, and is 5 mass% or less.

Furthermore, the compound represented by the general formula (N-1-2) is a compound selected from the compound group represented by the formula (N-1-2.1) to the formula (N-1-2.22). It is preferable that the formula (N-1-2.3) to the formula (N-1-2.7), the formula (N-1-2.10), the formula (N-1-2.11), the formula It is preferable that it is a compound represented by (N-1-2.13) and a formula (N-1-2.20), and when importance is attached to the improvement of Δε, the formula (N-1-2.3) is preferably a compound represented by the formula (N-1-2.7) _from when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) And a compound represented by the formula (N-1-2.13), and when emphasizing improvement in response speed, the compound represented by the formula (N-1-2.20) Is preferred.

  The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.22) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount of the product is 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, and 17% by mass. % Or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, 35% by mass That's it. The upper limit of the preferable content is 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, and 33% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass Or less, 13 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, 3 mass% or less It is.

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

(In the formula, R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. ^RN132 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 preferably a 1-propenyl group, an ethoxy group, a propoxy group, or a butoxy group. .

  Although the compound represented by general formula (N-1-3) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-3) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

  Furthermore, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.21). It is preferable that it is a compound represented by Formulas (N-1-3.1) to (N-1-3.7) and Formula (N-1-3.21), and Formula (N -1-3.1), Formula (N-1-3.2), Formula (N-1-3.3), Formula (N-1-3.4), and Formula (N-1-3.6) ) Is preferred.

  Compounds represented by formula (N-1-3.1) to formula (N-1-3.4), formula (N-1-3.6) and formula (N-1-3.21) are singly used. Can be used in combination or in combination, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3) ), A formula (N-1-3.4), and a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferable content of these compounds alone or with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, 13% by mass or more, and 15% by mass or more. It is 17 mass% or more and is 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N).)
Independently R ^N141 and ^{R N142} are each an alkyl group having 1 to 5 carbon atoms, preferably an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5, methyl group, propyl group, ethoxy Group or butoxy group is preferred.

  Although the compound represented by general formula (N-1-4) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the composition of the present embodiment is 3% by mass or more, 5% by mass or more, and 7% by mass. % Or more, 10 mass% or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 11% by mass or less, 10% by mass or less, and 8% by mass. It is as follows.

  Furthermore, the compound represented by the general formula (N-1-4) is a compound selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14). It is preferable that it is a compound represented by Formula (N-1-4.1) to (N-1-4.4), and Formula (N-1-4.1) and Formula (N -1-4.2) and compounds represented by formula (N-1-4.4) are preferred.

  The compounds represented by the formulas (N-1-4.1) to (N-1-4.14) can be used alone or in combination, but the composition of the present embodiment The lower limit of the preferred content of these compounds alone or with respect to the total amount of is 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, and 13% by mass These are 15% by mass or more, 17% by mass or more, and 20% by mass or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, 11% by mass or less, 10% by mass or less, and 8% by mass. It is as follows.

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

(In the formula, R ^N151 and R ^N152 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N151 and R ^N152 are 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, and preferably an ethyl group, a propyl group, or a butyl group. Is preferred.

  Although the compound represented by general formula (N-1-5) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-5) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 8% by mass or more, and 10% by mass. % Or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, and 25% by mass with respect to the total amount of the composition of the present embodiment. %, 23 mass% or less, 20 mass% or less, 18 mass% or less, 15 mass% or less, and 13 mass% or less.

  Furthermore, the compound represented by the general formula (N-1-5) is a compound selected from the compound group represented by the formula (N-1-5.1) to the formula (N-1-5.6). It is preferable that the compound represented by Formula (N-1-5.1), Formula (N-1-5.2), and Formula (N-1-5.4) is preferable.

  The compounds represented by formula (N-1-5.1), formula (N-1-5.2) and formula (N-1-5.4) may be used alone or in combination. However, the lower limit of the preferable content of these compounds alone or with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 8% by mass or more, and 10% by mass or more. Yes, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, and 25% by mass with respect to the total amount of the composition of the present embodiment. %, 23 mass% or less, 20 mass% or less, 18 mass% or less, 15 mass% or less, and 13 mass% or less.

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

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-10) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of compound to be used is, for example, one kind as one embodiment of this embodiment, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, setting the content higher is more effective. When emphasizing _TNI , the content is high. Setting to a higher value is more effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-10) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

  Furthermore, the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.21). It is preferable to be represented by formulas (N-1-10.1) to (N-1-10.5), formula (N-1-10.20), and formula (N-1-10.21). It is preferable that it is a compound, Formula (N-1-10.1), Formula (N-1-10.2), Formula (N-1-10.20), and Formula (N-1-10.21) The compound represented by these is preferable.

  The compounds represented by formula (N-1-10.1), formula (N-1-10.2), formula (N-1-10.20) and formula (N-1-10.21) are single Can be used in combination with each other, but the lower limit of the preferred content of these compounds alone or with respect to the total amount of the composition of the present embodiment is 5% by mass or more. It is at least 13% by mass, at least 15% by mass, at least 17% by mass, and at least 20% by mass. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-11) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, setting the content lower is more effective, and when emphasizing _TNI , the content. Setting to a higher value is more effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by Formula (N-1-11) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

  Furthermore, the compound represented by the general formula (N-1-11) is a compound selected from the group of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15). It is preferable that it is a compound represented by Formula (N-1-11.1) to (N-1-11.15), and Formula (N-1-11.2 and Formula (N- The compound represented by 1-11.4) is preferable.

  The compounds represented by the formula (N-1-11.2) and the formula (N-1-11.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount of the product is 5% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, and 17% by mass. % Or more and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1121 and R ^N1122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. ^RN1122 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-12) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1131 and R ^N1132 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-13) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-13) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1141 and R ^N1142 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N).)
R ^N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-14) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of compound to be used is, for example, one kind as one embodiment of this embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1151 and R ^N1152 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1152 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-15) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-15) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1161 and R ^N1162 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-16) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-16) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1171 and R ^N1172 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
^RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1172 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-17) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-17) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

( ^Wherein , R ^N1181 and R ^N1182 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group or a butyl group. ^RN1182 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 preferably an ethoxy group, a propoxy group, or a butoxy group.

  Although the compound represented by general formula (N-1-18) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by Formula (N-1-18) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

  Furthermore, the compound represented by the general formula (N-1-18) is a compound selected from the group of compounds represented by the formula (N-1-18.1) to the formula (N-1-18.5). It is preferable that it is a compound represented by Formula (N-18.1) to (N-1-11.3), and Formula (N-1-18.2 and Formula (N- The compound represented by 1-18.3) is preferable.

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

(In the formula, R ^N1201 and R ^N1202 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N)).
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 preferably an ethyl group, a propyl group, or a butyl group.

  Although the compound represented by general formula (N-1-20) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-20) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

(In the formula, R ^N1211 and R ^N1212 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
R ^N1211 and R ^N1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.

  Although the compound represented by general formula (N-1-21) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the composition of the present embodiment is 5% by mass or more, 10% by mass or more, and 13% by mass. % Or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. %, 20% or less, 18% or less, 15% or less, and 13% or less.

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

( ^Wherein , R ^N1221 and R ^N1222 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N)).
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 preferably an ethyl group, a propyl group, or a butyl group.

  Although the compound represented by general formula (N-1-22) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 35% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, and 23% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 20 mass% or less, 18 mass% or less, 15 mass% or less, 13 mass% or less, 10 mass% or less, and 5 mass% or less.

  Furthermore, the compound represented by the general formula (N-1-22) is a compound selected from the group of compounds represented by the formula (N-1-22.1) to the formula (N-1-22.12). It is preferable that it is a compound represented by Formula (N-1-22.1) to (N-1-22.5), and Formula (N-1-22.1) to (N- The compound represented by 1-22.4) is preferable.

  The compound represented by General Formula (N-3) is preferably a compound selected from the group of compounds represented by General Formula (N-3-2).

(In the formula, R ^N321 and R ^N322 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (N).)
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 preferably a propyl group or a pentyl group.

  Although the compound represented by general formula (N-3-2) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (N-3-2) with respect to the total amount of the composition of the present embodiment is 3% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass These are 30% by mass or more, 33% by mass or more, and 35% by mass or more. The upper limit of the preferable content is 50% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, and 33% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 30% by mass or less, 28% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass Or less, 13 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, and 5 mass% or less.

  Furthermore, the compound represented by the general formula (N-3-2) is a compound selected from the group of compounds represented by the formula (N-3-2.1) to the formula (N-3-2.3). Preferably there is.

  The liquid crystal composition has the general formula (L):

You may further contain the compound represented by these.

In formula (L),
R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently May be substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^L1 represents 0, 1, 2, or 3,
A ^L1 , A ^L2 and A ^L3 are each independently
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be substituted with —N═), and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group) Alternatively, one —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be substituted with —N═. .)
The group (a), the group (b) and the group (c) are each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, — OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different from each other, and when n ^L1 is 2 or 3, and a plurality of Z ^L2 are present, They may be the same or different from each other, but exclude the compounds represented by the general formulas (N-1), (N-2) and (N-3).

  The compound represented by the general formula (L) corresponds to a dielectrically neutral compound (Δε value is −2 to 2). Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of compound to be used is, for example, one kind as one embodiment. Alternatively, in another embodiment, there are 2 types, 3 types, 4 types, 5 types, 6 types, 7 types, 8 types, 9 types, 10 types or more is there.

  In the composition of the present embodiment, the content of the compound represented by the general formula (L) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability, dripping marks, image sticking. Therefore, it is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 10% by mass or more, and 20% by mass or more. 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, It is 75 mass% or more, and is 80 mass% or more. The upper limit of the preferable content is 95% by mass or less, 85% by mass or less, 75% by mass or less, 65% by mass or less, 55% by mass or less, and 45% by mass or less, It is 35 mass% or less, and is 25 mass% or less.

  When a composition having a low response speed and a high response speed is required, the lower limit value is high and the upper limit value is preferably high. Furthermore, when the composition of the present embodiment has a high Tni and requires a composition having good temperature stability, the above lower limit value is preferably high and the upper limit value is preferably high. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.

When importance is attached to reliability, R ^L1 and R ^L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.

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

R ^L1 and R ^L2 are a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R ^L1 is bonded is a phenyl group (aromatic). When the ring structure to which the alkoxy group and the alkenyl group having 4 to 5 carbon atoms are bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a straight chain having 1 to 5 carbon atoms is preferable. An alkyl group, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

  The alkenyl group is preferably selected from groups represented by any of the 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, 2 or 3 is preferred for improving the upper limit temperature of the nematic phase, and 1 is preferred for balancing these. In order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 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 -Preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and has the following structure:

Is more preferable, and a trans-1,4-cyclohexylene group or a 1,4-phenylene group is more preferable.

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

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

  The compound represented by the general formula (L) is preferably a compound selected from the group of compounds represented by the general formulas (L-1) to (L-7).

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

(In the formula, R ^L11 and R ^L12 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L11 and R ^L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

  Although the compound represented by general formula (L-1) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  The lower limit of the preferable content is 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, and 7% by mass with respect to the total amount of the composition of the present embodiment. %, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, 40 mass% These are 45% by mass or more, 50% by mass or more, and 55% by mass or more. The upper limit of the preferable content is 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, and 75% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 40% by mass Or less, 35% by mass or less, 30% by mass or less, and 25% by mass or less.

  When a composition having a low response speed and a high response speed is required, the lower limit value is high and the upper limit value is preferably high. Furthermore, when the composition of the present embodiment has a high Tni and a composition having good temperature stability is required, the above lower limit value is preferably moderate and the upper limit value is moderate. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

  The compound represented by General Formula (L-1) is preferably a compound selected from the group of compounds represented by General Formula (L-1-1).

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The compound represented by the general formula (L-1-1) is a compound selected from the group of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3). Is preferable, and is preferably a compound represented by the formula (L-1-1.2) or the formula (L-1-1.3), and particularly represented by the formula (L-1-1.3). It is preferable that it is a compound.

  The lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, and 2% by mass or more, It is 3 mass% or more, 5 mass% or more, 7 mass% or more, and 10 mass% or more. The upper limit of the preferable content is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 8% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, and 3 mass% or less.

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

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 15% by weight or more, 17% by weight or more, 20% by weight or more, 23% by weight or more, 25% by weight or more, 27% by weight or more, 30% by weight It is above, and it is 35 mass% or more. The upper limit of the preferable content is 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 42% by mass with respect to the total amount of the composition of the present embodiment. %, 40% or less, 38% or less, 35% or less, 33% or less, and 30% or less.

  Furthermore, the compound represented by the general formula (L-1-2) is a compound selected from the group of compounds represented by the formula (L-1-2.1) to the formula (L-1-2.4). It is preferable that it is a compound represented by Formula (L-1-2.2) to Formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because the response speed of the composition of the present embodiment is particularly improved. Moreover, when calculating | requiring Tni higher than a response speed, it is preferable to use the compound represented by a formula (L-1-2.3) or a formula (L-1-2.4). The content of the compounds represented by the formulas (L-1-2.3) and (L-1-2.4) is not preferably 30% by mass or more in order to improve the solubility at low temperatures. .

  The lower limit of the preferable content of the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition of the present embodiment is 10% by mass or more and 15% by mass or more, 18% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, 35 It is at least mass%, at least 38 mass%, and at least 40 mass%. The upper limit of the preferable content is 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 43% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 40% or less, 38% or less, 35% or less, 32% or less, 30% or less, 27% or less, 25% or less Or less and 22% by mass or less.

  The preferred total content of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the composition of the present embodiment The lower limit is 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, and 35% by mass or more. It is 40 mass% or more. The upper limit of the preferable content is 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 43% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 40% or less, 38% or less, 35% or less, 32% or less, 30% or less, 27% or less, 25% or less Or less and 22% by mass or less.

  The compound represented by General Formula (L-1) is preferably a compound selected from the group of compounds represented by General Formula (L-1-3).

(In the formula, R ^L13 and R ^L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L13 and R ^L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

  The lower limit of the preferable content of the compound represented by Formula (L-1-3) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, 20 mass% or more, 23 mass% or more, 25 mass% or more, 30 mass% That's it. The upper limit of the preferable content is 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 40% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 37% or less, 35% or less, 33% or less, 30% or less, 27% or less, 25% or less, 23% or less Or less, 20% by mass or less, 17% by mass or less, 15% by mass or less, 13% by mass or less, and 10% by mass or less.

  Furthermore, the compound represented by the general formula (L-1-3) is a compound selected from the group of compounds represented by the formula (L-1-3.1) to the formula (L-1-3.13). Preferably, it is a compound represented by the formula (L-1-3.1), the formula (L-1-3.3) or the formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because the response speed of the composition of the present embodiment is particularly improved. Moreover, when calculating | requiring Tni higher than a response speed, Formula (L-1-3.3), Formula (L-1-3.4), Formula (L-1-3.11), and Formula (L- It is preferable to use a compound represented by 1-3.12). Sum of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) The content of is not preferably 20% or more in order to improve the solubility at low temperatures.

  The lower limit of the preferable content of the compound represented by Formula (L-1-3.1) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, and 2% by mass or more. 3% or more, 5% or more, 7% or more, 10% or more, 13% or more, 15% or more, 18% or more, 20% It is at least mass%. The upper limit of the preferable content is 20% by mass or less, 17% by mass or less, 15% by mass or less, 13% by mass or less, and 10% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 8 mass% or less, 7 mass% or less, and 6 mass% or less.

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

(In the formula, R ^L15 and R ^L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L15 and R ^L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

  The lower limit of the preferable content of the compound represented by Formula (L-1-4) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 25% by mass or less, 23% by mass or less, 20% by mass or less, 17% by mass or less, and 15% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 13 mass% or less, and 10 mass% or less.

  The lower limit of the preferable content of the compound represented by the formula (L-1-5) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 13 mass% or more, 15 mass% or more, 17 mass% or more, and 20 mass% or more. The upper limit of the preferable content is 25% by mass or less, 23% by mass or less, 20% by mass or less, 17% by mass or less, and 15% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 13 mass% or less, and 10 mass% or less.

  Furthermore, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-4.3) and ( A compound selected from the group of compounds represented by formula (L-1-5.3) to formula (L-1-5.3) is preferred, and formula (L-1-4.2) or formula (L- It is preferable that it is a compound represented by 1-5.2).

  The lower limit of the preferable content of the compound represented by the formula (L-1-4.2) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, and 2% by mass or more, 3% or more, 5% or more, 7% or more, 10% or more, 13% or more, 15% or more, 18% or more, 20% It is at least mass%. The upper limit of the preferable content is 20% by mass or less, 17% by mass or less, 15% by mass or less, 13% by mass or less, and 10% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 8 mass% or less, 7 mass% or less, and 6 mass% or less.

  Formula (L-1-1.3), Formula (L-1-2.2), Formula (L-1-3.1), Formula (L-1-3.3), Formula (L-1- 3.4), two or more compounds selected from the compounds represented by formula (L-1-3.11) and formula (L-1-3.12) are preferably combined. -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-4.2). The lower limit of the preferable content of the total content of these compounds is 1% by mass or more, 2% by mass or more, 3% by mass or more, based on the total amount of the composition of the present embodiment, 5 % By mass, 7% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 23% by mass % Or more, 25% by mass or more, 27% by mass or more, 30% by mass or more, 33% by mass or more, and 35% by mass or more. The upper limit of the preferable content is 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, and 45% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 40% by mass or less, 37% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 25% by mass Or less, 23% by mass or less, and 20% by mass or less.

  When emphasizing the reliability of the composition, compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (L-1-1.3) and (L-1-2.2) when importance is attached to the response speed of the composition. It is preferable to combine two or more compounds selected from the following compounds.

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

(In the formula, R ^L17 and R ^L18 each independently represent a methyl group or a hydrogen atom.)
The lower limit of the preferable content of the compound represented by the formula (L-1-6) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 5% by mass or more, and 10% by mass. % Or more, 15% by weight or more, 17% by weight or more, 20% by weight or more, 23% by weight or more, 25% by weight or more, 27% by weight or more, 30% by weight It is above, and it is 35 mass% or more. The upper limit of the preferable content is 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, and 42% by mass with respect to the total amount of the composition of the present embodiment. %, 40% or less, 38% or less, 35% or less, 33% or less, and 30% or less.

  Furthermore, the compound represented by the general formula (L-1-6) is a compound selected from the group of compounds represented by the formula (L-1-6.1) to the formula (L-1-6.3). Preferably there is.

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

(In the formula, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. The alkoxy group of number 1-4 is preferable.

  Although the compound represented by general formula (L-1) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  When emphasizing solubility at low temperatures, the effect is high when the content is set to be large. On the other hand, when the response speed is important, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  The lower limit of the preferable content of the compound represented by the formula (L-2) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. It is 5 mass% or more, 7 mass% or more, and 10 mass% or more. The upper limit of the preferable content is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 8% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, and 3 mass% or less.

  Furthermore, the compound represented by the general formula (L-2) is preferably a compound selected from the group of compounds represented by the formula (L-2.1) to the formula (L-2.6). It is preferable that it is a compound represented by (L-2.1), Formula (L-2.3), Formula (L-2.4), and Formula (L-2.6).

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

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

  Although the compound represented by general formula (L-3) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  The lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. It is 5 mass% or more, 7 mass% or more, and 10 mass% or more. The upper limit of the preferable content is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 8% by mass with respect to the total amount of the composition of the present embodiment. % Or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, and 3 mass% or less.

  When a high birefringence is obtained, the effect is high when the content is set to be large. On the other hand, when high Tni is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

  Furthermore, the compound represented by General Formula (L-3) is preferably a compound selected from the group of compounds represented by Formula (L-3.1) to Formula (L-3.7). A compound represented by formula (L-3.7) from (L-3.2) is preferable.

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

(In the formula, R ^L41 and R ^L42 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. The alkoxy group of number 1-4 is preferable. )
Although the compound represented by general formula (L-4) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  In the composition of the present embodiment, the content of the compound represented by the general formula (L-4) is low-temperature solubility, transition temperature, electrical reliability, birefringence index, process suitability, dropping trace. Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. 5% or more, 7% or more, 10% or more, 14% or more, 16% or more, 20% or more, 23% or more Yes, 26% by mass or more, 30% by mass or more, 35% by mass or more, and 40% by mass or more. The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present embodiment is 50% by mass or less, 40% by mass or less, and 35% by mass or less. 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and 5% by mass or less.

  The compound represented by the general formula (L-4) is preferably, for example, a compound represented by the formula (L-4.1) to the formula (L-4.3).

  Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by the formula (L-4.1) is contained, the formula (L Even if the compound represented by -4.2) is contained, both the compound represented by formula (L-4.1) and the compound represented by formula (L-4.2) are contained. Or all of the compounds represented by formula (L-4.1) to formula (L-4.3) may be included.

  The lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) with respect to the total amount of the composition of the present embodiment is 3% by mass or more, 5 mass% or more, 7 mass% or more, 9 mass% or more, 11 mass% or more, 12 mass% or more, 13 mass% or more, 18 mass% or more, 21 It is at least mass%. The upper limit of the preferable content is 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, and 23% by mass or less, It is 20 mass% or less, 18 mass% or less, 15 mass% or less, 13 mass% or less, 10 mass% or less, and 8 mass% or less.

  When both the compound represented by Formula (L-4.1) and the compound represented by Formula (L-4.2) are contained, both compounds with respect to the total amount of the composition of this embodiment The lower limit of the preferable content is 15% by mass or more, 19% by mass or more, 24% by mass or more, and 30% by mass or more. The upper limit of the preferable content is 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, and 23% by mass or less, It is 20 mass% or less, 18 mass% or less, 15 mass% or less, and 13 mass% or less.

  The compound represented by General Formula (L-4) is preferably, for example, a compound represented by Formula (L-4.4) to Formula (L-4.6), and Formula (L-4.4). It is preferable that it is a compound represented by this.

  Depending on required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by formula (L-4.4) is contained, formula (L -4.5) contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5). It may be.

  The lower limit of the preferable content of the compound represented by Formula (L-4.4) or Formula (L-4.5) with respect to the total amount of the composition of the present embodiment is 3% by mass or more, 5 mass% or more, 7 mass% or more, 9 mass% or more, 11 mass% or more, 12 mass% or more, 13 mass% or more, 18 mass% or more, 21 It is at least mass%. Preferred upper limit values are 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 23% by mass or less, and 20% by mass. Or less, 18 mass% or less, 15 mass% or less, 13 mass% or less, 10 mass% or less, and 8 mass% or less.

  When both the compound represented by Formula (L-4.4) and the compound represented by Formula (L-4.5) are contained, both compounds with respect to the total amount of the composition of this embodiment The lower limit of the preferred content is 15% by mass or more, 19% by mass or more, 24% by mass or more, 30% by mass or more, and the preferred upper limit is 45% by mass or less. 15% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass % Or less and 13 mass% or less.

  The compound represented by General Formula (L-4) is preferably a compound represented by Formula (L-4.7) to Formula (L-4.10), and in particular, Formula (L-4. The compound represented by 9) is preferred.

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

(In the formula, R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. The alkoxy group of number 1-4 is preferable.

  Although the compound represented by general formula (L-5) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  In the composition of the present embodiment, the content of the compound represented by the general formula (L-5) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, and drop marks. Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. 5% or more, 7% or more, 10% or more, 14% or more, 16% or more, 20% or more, 23% or more Yes, 26% by mass or more, 30% by mass or more, 35% by mass or more, and 40% by mass or more. The upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the composition of the present embodiment is 50% by mass or less, 40% by mass or less, and 35% by mass or less. 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and 5% by mass or less The compound represented by the general formula (L-5) is The compound represented by formula (L-5.1) or formula (L-5.2) is preferred, and the compound represented by formula (L-5.1) is particularly preferred.

  The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, 3% by mass or more, and 5% by mass or more. 7% by mass or more. The upper limit of preferable content of these compounds is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 9% by mass or less.

  The compound represented by General Formula (L-5) is preferably a compound represented by Formula (L-5.3) or Formula (L-5.4).

  The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, 3% by mass or more, and 5% by mass or more. 7% by mass or more. The upper limit of preferable content of these compounds is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 9% by mass or less.

  The compound represented by the general formula (L-5) is preferably a compound selected from the group of compounds represented by the formula (L-5.5) to the formula (L-5.7). It is preferable that it is a compound represented by L-5.7).

  The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, 3% by mass or more, and 5% by mass or more. 7% by mass or more. The upper limit of preferable content of these compounds is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 9% by mass or less.

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

(In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L), and 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, and one of X ^L61 and X ^L62 is a fluorine atom and the other is a hydrogen atom. It is preferable.

  Although the compound represented by general formula (L-6) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. 5% or more, 7% or more, 10% or more, 14% or more, 16% or more, 20% or more, 23% or more Yes, 26% by mass or more, 30% by mass or more, 35% by mass or more, and 40% by mass or more. The upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the composition of the present embodiment is 50% by mass or less, 40% by mass or less, and 35% by mass or less. 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and 5% by mass or less. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

  The compound represented by General Formula (L-6) is preferably a compound represented by Formula (L-6.1) to Formula (L-6.9).

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It is preferable to contain 1 type-3 types from these compounds, and it is more preferable to contain 1 type-4 types. Further, since the wide molecular weight distribution of the compound to be selected is also effective for solubility, for example, one type of the compound represented by the formula (L-6.1) or (L-6.2), the formula (L- 6.4) or one type from the compound represented by (L-6.5), one type from the compound represented by formula (L-6.6) or formula (L-6.7), formula (L It is preferable to select one compound from the compounds represented by -6.8) or (L-6.9) and combine them as appropriate. Among these, it is represented by Formula (L-6.1), Formula (L-6.3), Formula (L-6.4), Formula (L-6.6), and Formula (L-6.9). It is preferable to include a compound.

  Furthermore, the compound represented by the general formula (L-6) is preferably a compound represented by the formula (L-6.10) to the formula (L-6.17), for example. The compound represented by L-6.11) is preferable.

  The lower limit of the preferable content of these compounds with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, 3% by mass or more, and 5% by mass or more. 7% by mass or more. The upper limit of preferable content of these compounds is 20% by mass or less, 15% by mass or less, 13% by mass or less, 10% by mass or less, and 9% by mass or less.

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

^{(Wherein, R L71} and ^{R L72} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), A L71} and ^{A L72} is ^{A L2} and in the general formula (L) independently A ^L3 represents the same meaning, but the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, Z ^L71 represents 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, and A ^L71 and A ^L72. Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, and Z ^L71 is a single group. A bond or COO- is preferable, a single bond is preferable, and X ^L71 and X ^L72 are preferably a hydrogen atom.

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It combines according to performance requested | required, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The kind of the compound to be used is, for example, one kind, two kinds, three kinds, and four kinds as one embodiment.

  In the composition of the present embodiment, the content of the compound represented by the general formula (L-7) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability, dripping marks. Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

  The lower limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 2% by mass or more, and 3% by mass or more. 5% or more, 7% or more, 10% or more, 14% or more, 16% or more, and 20% or more. The upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present embodiment is 30% by mass or less, 25% by mass or less, and 23% by mass or less. It is 20 mass% or less, 18 mass% or less, 15 mass% or less, 10 mass% or less, and 5 mass% or less.

  When an embodiment with high Tni is desired for the composition of the present embodiment, it is preferable to increase the content of the compound represented by formula (L-7), and when an embodiment with a low viscosity is desired, It is preferable to reduce the amount.

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7.1) to Formula (L-7.4), and Formula (L-7. It is preferable that it is a compound represented by 2).

  Furthermore, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.11) to the formula (L-7.13), and the formula (L-7. It is preferable that it is a compound represented by 11).

  Furthermore, the compound represented by the general formula (L-7) is a compound represented by the formula (L-7.21) to the formula (L-7.23). A compound represented by the formula (L-7.21) is preferable.

  Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.31) to the formula (L-7.34), and the formula (L-7. 31) or / and a compound represented by the formula (L-7.32).

  Furthermore, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.41) to the formula (L-7.44), and the formula (L-7. 41) or / and a compound represented by formula (L-7.42).

  Furthermore, the compound represented by General Formula (L-7) is preferably a compound represented by Formula (L-7.51) to Formula (L-7.53).

  The liquid crystal composition may further contain a polymerizable compound. The polymerizable compound may be a known polymerizable compound used for a liquid crystal composition. Examples of the polymerizable compound include the general formula (P):

The compound represented by these is mentioned.

In formula (P),
Z ^p1 represents a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, or the number of carbon atoms in which the hydrogen atom may be substituted with a halogen atom. An alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and an alkenyloxy group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom Represents the group or -Sp ^p2 -R ^p2 ,
R ^p1 and R ^p2 are the following formulas (R-I) to (R-IX):

(Where
* Binds to Sp ^p1 ,
R ^{2 to} R ⁶ 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,
W represents a single bond, —O— or a methylene group,
T represents a single bond or —COO—;
p, t, and q each independently represents 0, 1, or 2. )
Represents one of the following:
Sp ^p1 and Sp ^p2 represent spacer groups,
L ^p1 and L ^p2 each independently represent 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 ^a —, —NR ^a —CO—, —SCH ₂ —, —CH ₂ S ^{-, - CH = CR a -COO} -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - COO-CR a = CH-COO -, - ^{COO-CR a = CH-OCO} -, - OCO-CR a = CH-COO -, - OCO-CR a = CH-OCO -, - (CH 2) z -C (= O) -O -, - ( _{CH 2) z -O- (C =} O) -, - O- (C = O) - (CH 2) z -, - (C = O _{-O- (CH 2) z -,} - 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 each R ^a is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z represents an integer of 1 to 4, and
M ^p2 represents 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2, 5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5 -Represents a diyl group or a single bond, but M ^p2 is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms , ^May be substituted with a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a nitro group or —R ^p1 ,
M ^p1 represents the following formulas (i-11) to (ix-11):

(In the formula, * binds to Sp ^p1 and ** binds to L ^p1 , L ^p2 or Z ^p1 .)
Represents one of the following:
Any hydrogen atom on M ^p1 is an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogenated group having 1 to 12 carbon atoms. ^May be substituted with an alkoxy group, a halogen atom, a cyano group, a nitro group or —R ^p1 ;
M ^p3 represents the following formulas (i-13) to (ix-13):

(In the formula, * binds to Z ^p1 and ** binds to L ^p2 .)
Represents one of the following:
Any hydrogen atom on M ^p3 is an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogenated group having 1 to 12 carbon atoms. ^May be substituted with an alkoxy group, a halogen atom, a cyano group, a nitro group or —R ^p1 ;
m ^{p2 to} m ^p4 each independently represents 0, 1, 2, or 3,
m ^p1 and m ^p5 each independently represent 1, 2 or 3;
When a plurality of Z ^p1 are present, they may be the same as or different from each other. When a plurality of R ^p1 are present, they may be the same as or different from each other, and a plurality of R ^p2 are present. When present, they may be the same as or different from each other. When a plurality of Sp ^p1 are present, they may be the same as or different from each other. When there are a plurality of Sp ^{p2 May} be the same or different from each other, and when a plurality of L ^p1 are present, they may be the same or different from each other, and when a plurality of M ^p2 are present, they are They may be the same or different.

When the liquid crystal composition of this embodiment further contains a polymerizable compound in addition to a compound in which a monovalent organic group having a group represented by K ⁱ¹ is substituted on cyclophane, the pretilt angle of the liquid crystal molecules is preferably Can be formed.

  The composition of the present embodiment preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.

  When emphasizing the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% by mass or less, and preferably 3% by mass or less with respect to the total mass of the composition. More preferably, it is more preferably 1% by mass or less, and most preferably not substantially contained.

  When importance is attached to stability by UV irradiation, the content of the compound substituted with chlorine atoms is preferably 15% by mass or less, preferably 10% by mass or less, based on the total mass of the composition. 8% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably substantially not contained.

  It is preferable to increase the content of a compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80% of the total mass of the composition. It is preferably at least 90% by mass, more preferably at least 90% by mass, even more preferably at least 95% by mass, and it is composed of only a compound having substantially all 6-membered ring structures in the molecule. Most preferably it constitutes a product.

  In order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group relative to the total mass of the composition. It is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. Further preferred.

  When importance is attached to improvement of viscosity and improvement of Tni, the content of a compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which a hydrogen atom may be substituted with a halogen, may be reduced. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total mass of the composition. It is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably substantially not contained.

  In this specification, it does not contain substantially means that it does not contain except the thing (unavoidable impurity) contained unintentionally.

The lower limit of the average elastic constant (K _AVG ) of the liquid crystal composition is preferably 10 or more, preferably 10.5 or more, preferably 11 or more, preferably 11.5 or more, preferably 12 or more, and 12.3 or more. Preferably, 12.5 or more is preferable, 12.8 or more is preferable, 13 or more is preferable, 13.3 or more is preferable, 13.5 or more is preferable, 13.8 or more is preferable, 14 or more is preferable, 14.3 Or more, preferably 14.5 or more, preferably 14.8 or more, preferably 15 or more, preferably 15.3 or more, preferably 15.5 or more, preferably 15.8 or more, preferably 16 or more, 16 .3 or more, preferably 16.5 or more, preferably 16.8 or more, preferably 17 or more, preferably 17.3 or more, preferably 17.5 or more, 7.8 or more, 18 or more. The upper limit of the average elastic constant (K _AVG ) of the liquid crystal composition is preferably 25 or less, preferably 24.5 or less, preferably 24 or less, preferably 23.5 or less, preferably 23 or less, and 22.8 or less. Preferably, 22.5 or less is preferable, 22.3 or less is preferable, 22 or less is preferable, 21.8 or less is preferable, 21.5 or less is preferable, 21.3 or less is preferable, 21 or less is preferable, 20.8 or less The following is preferable, 20.5 or less is preferable, 20.3 or less is preferable, 20 or less is preferable, 19.8 or less is preferable, 19.5 or less is preferable, 19.3 or less is preferable, 19 or less is preferable, 18 .8 or less is preferred, 18.5 or less is preferred, 18.3 or less is preferred, 18 or less is preferred, 17.8 or less is preferred, 17.5 or less is preferred, Preferably 7.3 or less, 17 or less. When importance is placed on reducing power consumption, it is effective to reduce the amount of light from the backlight, and it is preferable to improve the light transmittance of the liquid crystal display element. For this purpose, the value of K _AVG should be set low. preferable. It is preferable to set a higher value of K _AVG in the case of emphasizing improved response speed.
(Liquid crystal display element)
The liquid crystal composition of this embodiment is applied to a liquid crystal display element. Hereinafter, an example of the liquid crystal display element according to the present embodiment will be described with reference to FIGS.

  FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, for convenience of explanation, each component is shown separated. As shown in FIG. 1, the liquid crystal display element 1 according to the present embodiment is provided between a first substrate 2 and a second substrate 3 disposed so as to face each other, and between the first substrate 2 and the second substrate 3. The liquid crystal layer 4 is composed of the liquid crystal composition of the present embodiment described above.

  A pixel electrode layer 5 is formed on the surface of the first substrate 2 on the liquid crystal layer 4 side. A common electrode layer 6 is formed on the second substrate 3 on the liquid crystal layer 4 side. The first substrate 2 and the second substrate 3 may be sandwiched between a pair of polarizing plates 7 and 8. A color filter 9 may be further provided on the liquid crystal layer 4 side of the second substrate 3.

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

  The first substrate 2 and the second substrate 3 are made of a flexible material such as glass or plastic. At least one of the first substrate 2 and the second substrate 3 is formed of a transparent material, and the other may be formed of a transparent material or may be formed of an opaque material such as metal or silicon. The first substrate 2 and the second substrate 3 are bonded to each other by a sealing material and a sealing material such as an epoxy-based thermosetting composition disposed in the peripheral region, and in order to maintain a distance between the substrates. For example, granular spacers such as glass particles, plastic particles, and alumina particles, or spacer columns made of a resin formed by a photolithography method may be disposed.

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

  The color filter 9 preferably forms a black matrix from the viewpoint of preventing light leakage, and preferably forms a black matrix (not shown) in a portion corresponding to the thin film transistor.

  The black matrix may be installed with the color filter on the substrate opposite to the array substrate, or may be installed with the color filter on the array substrate side. The black matrix is on the array substrate, and the color filter is on the other substrate. It may be installed separately. In addition, the black matrix may be provided separately from the color filter, but the transmittance may be reduced by overlapping each color of the color filter.

  FIG. 2 is an enlarged plan view of a region surrounded by an I line that is a part of the pixel electrode layer 5 formed on the first substrate 2 in FIG. As shown in FIG. 2, in the pixel electrode layer 5 including the thin film transistor formed on the surface of the first substrate 2, a plurality of gate bus lines 11 for supplying scanning signals and a plurality of gate bus lines 11 for supplying display signals are provided. Data bus lines 12 are arranged in a matrix so as to cross each other. In FIG. 2, only a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12 are shown.

  A unit pixel of the liquid crystal display element is formed by a region surrounded by the plurality of gate bus lines 11 and the plurality of data bus lines 12, and a pixel electrode 13 is formed in the unit pixel. The pixel electrode 13 has a so-called fishbone structure that includes two trunks that are orthogonal to each other and have a cross shape, and a plurality of branches extending from each trunk. Further, a Cs electrode 14 is provided between the pair of gate bus lines 11, 11 substantially in parallel with the gate bus line 11. A thin film transistor including a source electrode 15 and a drain electrode 16 is provided in the vicinity of the 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 each preferably formed of a metal film, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or an alloy thereof. More preferably, it is made of Mo, Al or an alloy thereof.

  The pixel electrode 13 is preferably a transparent electrode in order to improve the transmittance. The transparent electrode is formed by sputtering an oxide semiconductor (ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, AZTO (AlZnSnO), or the like). At this time, the film thickness of the transparent electrode may be 10 to 200 nm. In order to reduce the electrical resistance, the transparent electrode can be formed as a polycrystalline ITO film by baking an amorphous ITO film.

  In the liquid crystal display element of this embodiment, for example, wiring is formed on the first substrate 2 and the second substrate 3 by sputtering a metal material such as Al or an alloy thereof, and the pixel electrode layer 5 and the common electrode layer 6 are formed. Each can be formed. Further, the color filter 9 can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. Further, the color filter 9 may be provided on the side of the substrate having TFTs or the like.

  The first substrate 2 and the second substrate 3 are opposed to each other so that the pixel electrode layer 5 and the common electrode layer 6 are on the inner side. At this time, the distance between the first substrate 2 and the second substrate 3 is interposed via a spacer. May be adjusted. At this time, it is preferable to adjust the thickness of the liquid crystal layer 4 to be, for example, 1 to 100 μm.

  When the polarizing plates 7 and 8 are used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal layer 4 and the thickness of the liquid crystal layer 4 so that the contrast is maximized. In addition, when there are two polarizing plates 7 and 8, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are improved. Furthermore, a retardation film for widening the viewing angle can also be used. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method for sandwiching the composition between the two substrates 2 and 3, a normal vacuum injection method or a drop drop (ODF) method can be used. Although it does not occur, it has a problem that the trace of implantation remains, but in the present embodiment, it can be suitably used for a display element manufactured using the ODF method. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal combination curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of the composition under air. In the present embodiment, in the ODF method, it is possible to suppress the occurrence of dropping marks when the liquid crystal composition is dropped on the substrate. In addition, a dripping mark is defined as a phenomenon in which a mark in which a liquid crystal composition is dripped appears white when displaying black.

  In addition, in the manufacturing process of the liquid crystal display element by the ODF method, it is necessary to drop an optimal liquid crystal injection amount according to the size of the liquid crystal display element, but the liquid crystal composition of the present embodiment is generated at the time of liquid crystal dropping, for example. The liquid crystal display element can be kept at a high yield because the liquid crystal can be stably dropped over a long period of time with little influence on a sudden pressure change or impact in the dropping device. In particular, small liquid crystal display elements frequently used in smartphones that have recently become popular are difficult to control the deviation from the optimal value within a certain range because the optimal liquid crystal injection amount is small. By using the composition, a stable discharge amount of the liquid crystal material can be realized even in a small liquid crystal display element.

  In the case where the liquid crystal composition of the present embodiment contains a polymerizable compound, an appropriate polymerization rate is desirable as a method for polymerizing the polymerizable compound in order to obtain good alignment performance of the liquid crystal. A method of polymerizing by irradiating active energy rays such as single, combined use or sequentially is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the polymerizable compound-containing composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given adequate transparency to the active energy rays. Don't be. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the polymerizable compound-containing composition. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In a horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present embodiment is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-ray to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. Energy of ultraviolet light irradiation, can be appropriately ^adjusted, preferably ^{10mJ / cm 2 ~500J / cm 2} , 100mJ / cm 2 ~200J / cm 2 is more preferable. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays.

  In the liquid crystal composition of the present embodiment, since the compound (i) does not inhibit the polymerization reaction of the polymerizable compound, the polymerizable compounds are suitably polymerized, and the unreacted polymerizable compound remains in the liquid crystal composition. Can be suppressed.

  For example, when the compound (ii) is used as the polymerizable compound, the obtained liquid crystal display element 1 includes two substrates 2 and 3, a liquid crystal composition provided between the two substrates 2 and 3, and a general formula And a liquid crystal layer 4 containing a polymer of the compound represented by (ii). In this case, the polymer of the compound represented by the general formula (ii) is considered to be unevenly distributed on the substrate 2 or 3 side in the liquid crystal layer 4.

  The liquid crystal display element 1 may be an active matrix driving liquid crystal display element. The liquid crystal display element 1 may be a PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type liquid crystal display element, and is preferably a PSA type liquid crystal display element.

  In the liquid crystal display element of this embodiment, since the liquid crystal composition containing the compound (i) is used, an alignment film such as a polyimide alignment film is provided on the liquid crystal layer 4 side of the first substrate 2 and the second substrate 3. There is no need to be. That is, the liquid crystal display element of this embodiment can take a configuration in which at least one of the two substrates does not have an alignment film such as a polyimide alignment film.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

Examples 1 to 20, Comparative Example 1 Production of calixarene compound Calixarene compounds (1) to (24) were produced by the procedure described below. The specific structures of the calixarene compounds (1) to (24) are as follows.

In the examples of the present application, the structure of the product was identified by ¹ H-NMR, ¹³ C-NMR, and FD-MS measured under the following conditions.

¹ H-NMR was measured using “JNM-ECM400S” manufactured by JEOL RESONANCE under the following conditions.

Magnetic field strength: 400MHz
Integration count: 16 times Solvent: Deuterated chloroform Sample concentration: 2 mg / 0.5 ml
¹³ C-NMR was measured under the following conditions using “JNM-ECM400S” manufactured by JEOL RESONANCE.

Magnetic field strength: 100 MHz
Integration count: 1000 times Solvent: Deuterated chloroform Sample concentration: 2 mg / 0.5 ml
FD-MS was measured under the following conditions using “JMS-T100GC AccuTOF” manufactured by JEOL Ltd.

Measurement range: m / z = 50.00 to 2000.00
Rate of change: 25.6 mA / min
Final current value: 40 mA
Cathode voltage: -10 kV

Example 1 Production of Calixarene Compound (1) <Production of Intermediate (M-1)>
A four-necked flask equipped with a stirrer, thermometer, and reflux condenser was charged with 50 g of tertiary butyl calix [4] arene represented by the following structural formula (a), 32.26 g of phenol and 350 ml of dehydrated toluene, and nitrogen. The mixture was stirred at 300 rpm in a flow environment. The tertiary butyl calix [4] arene was suspended without dissolving. The flask was immersed in an ice bath, and 51.37 g of anhydrous aluminum chloride (III) was added in several portions. The color of the solution changed to light orange and transparent, and anhydrous aluminum (III) chloride was precipitated at the bottom. After stirring at room temperature for 5 hours, the reaction mixture was transferred to a 1 L beaker, and the reaction was stopped by adding ice, 100 ml of 1N hydrochloric acid, and 350 ml of toluene. The color of the solution changed to light yellow and transparent. The reaction mixture was transferred to a separatory funnel and the organic layer was collected. The operation of adding 100 ml of toluene to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate, and then filtered. The solvent was distilled off with an evaporator to obtain a mixture of white crystals and a colorless transparent liquid. While stirring the mixture, methanol was slowly added to reprecipitate the product that had been dissolved in the liquid. After filtration with a Kiriyama funnel, the resulting white crystals were washed with methanol and then vacuum dried to obtain 29.21 g of an intermediate (M-1) represented by the following structural formula (b).

<Production of intermediate (M-2)>
In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 7.159 g of lauroyl chloride and 16.27 g of nitroethane were placed and stirred. The flask was immersed in an ice bath and 5.57 g of anhydrous aluminum chloride (III) was added in several portions. The solution became a pale orange clear solution. The mixture was stirred at room temperature for 30 minutes, and 2.30 g of the intermediate (M-1) was added in several portions. The reaction mixture foamed into an orange clear solution. After reacting at room temperature for 5 hours, the reaction mixture was slowly transferred to a 1 L beaker containing chloroform, ion-exchanged water and ice to stop the reaction. After adjusting the pH to 1 by adding 1N hydrochloric acid, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate, and then filtered. The solvent was distilled off with an evaporator to obtain a yellow transparent solution. The flask was immersed in an ice bath and methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the obtained white crystal was again dissolved in chloroform, and methanol was added and recrystallized. The obtained white crystals were vacuum-dried to obtain 5.00 g of an intermediate (M-2) represented by the following structural formula (c).

<Production of Intermediate (M-3)>
In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 7.00 g of the intermediate (M-2) and 81.44 g of diethylene glycol monoethyl ether were added and stirred. The inside of the flask became a white suspension. 2.585 g of hydrazine monohydrate was added and stirred. The flask became a colorless and transparent solution. After adding 6.809 g of potassium hydroxide pellets and stirring at 100 ° C. for 30 minutes, stirring was continued for 12 hours under reflux conditions. The inside of the flask was a yellow transparent solution. After cooling to 90 ° C., 30 g of ion exchange water was added, and the mixture was further stirred for 30 minutes. After cooling to room temperature, the reaction mixture was transferred to a beaker and adjusted to pH 1 by adding 6N hydrochloric acid. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and methanol was added to the resulting orange viscous liquid to reprecipitate the product. It filtered with the Kiriyama funnel, the obtained milky white crystal was vacuum-dried, and 4.156 g of intermediate bodies (M-3) represented by following Structural formula (d) were obtained.

<Production of calixarene compound (1)>
Into a four-necked flask equipped with a stirrer, thermometer and reflux condenser, the intermediate (M-3) 11.00 g, 72.11 g of tetrahydrofuran, 12.62 g of triphenylphosphine, and 15.65 g of hydroxyethyl methacrylate were placed. And stirred. The inside of the flask was an ocher suspension solution. The flask was immersed in an ice bath, and 8.92 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a red transparent solution. After completion of dropping, the mixture was stirred at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The reaction product was extracted with chloroform and then washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the obtained white crystal was vacuum-dried, and 7.95 g of calixarene compounds (1) were obtained.
Examples 2, 3 Production of calixarene compounds (2) and (3) <Production of intermediate (M-4)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 20.00 g of the intermediate (M-3), 180.00 g of anhydrous acetonitrile, 11.10 g of potassium carbonate, 22.30 g of methyl 2-bromoacetate And stirred for 20 hours under reflux conditions. After cooling to room temperature, the pH was adjusted to 6 by adding ion exchange water and 0.3N hydrochloric acid. 50 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 50 g of chloroform to the aqueous layer and extracting organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a milky white solid. After dissolving in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the milky-white crystal obtained was vacuum-dried, and the intermediate body (M-4) 23.89g represented by the following structural formula (e) was obtained.

<Production of Intermediate (M-5)>
Into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, the intermediate (M-4) 12.00 g and tetrahydrofuran 125.38 g were added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath and 2.63 g of lithium aluminum hydride was added. The flask became a gray suspension. The reaction was allowed to stir at room temperature for 6 hours. The flask was immersed in an ice bath, and 2 g of ion exchange water, 5 g of a 10% aqueous sodium hydroxide solution, 5 g, 20 g of ion exchange water, and 30 g of chloroform were added. The reaction solution was filtered through diatomaceous earth, and 1 g of 1N hydrochloric acid and 30 g of chloroform were added to the filtrate. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a colorless transparent liquid. Methanol was added to reprecipitate the product and filtered through a Kiriyama funnel. The obtained white crystals were vacuum-dried to obtain 8.63 g of an intermediate (M-5) represented by the following structural formula (f).

<Production of calixarene compounds (2) and (3)>
Into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.00 g of the intermediate (M-5), 6.80 g of tetrahydrofuran, 0.824 g of triphenylphosphine, and 0.270 g of methacrylic acid were added and stirred. did. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.635 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. After completion of dropping, the mixture was stirred at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) to obtain 0.521 g of calixarene compound (2) and calixarene compound (3 ) 0.754 g was obtained.
Examples 3 and 4 Production of calixarene compounds (3) and (4) In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.00 g of the intermediate (M-5), tetrahydrofuran 6. 80 g, 1.029 g of triphenylphosphine, and 0.338 g of methacrylic acid were added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.794 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. After completion of dropping, the mixture was stirred at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) to obtain 0.374 g of calixarene compound (3) and calixarene compound (4 ) 0.287 g was obtained.
Example 5 Production of Calixarene Compound (5) <Production of Intermediate (M-6)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2 g of the calixarene compound (1) and 12.00 g of dehydrated N, N-dimethylformamide were added and stirred. The flask was immersed in an ice bath and 0.181 g of sodium hydride (liquid paraffin 60 mass% dispersion) was slowly added. 7-[[(1,1-dimethylethyl) dimethylsilyl] oxy] -6-[[[(1,1-1,1-dimethylethyl) dimethylsilyl] oxy] methyl] -1-iodoheptane 2.272 g And stirred at room temperature for 20 hours. A yellow oily substance was deposited on the flask wall. Ion exchange water and 0.3N hydrochloric acid were added to adjust the pH to 6. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent: normal hexane: acetone = 95: 5), dried in vacuo, and colorless as represented by the following structural formula (g) 0.938 g of a transparent oily intermediate (M-6) was obtained.

<Production of calixarene compound (5)>
0.938 g of the intermediate (M-6) and 6.543 g of tetrahydrofuran were added to a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 3.63 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The inside of the flask was a pale red transparent solution. After stirring for 24 hours, the flask was immersed in an ice bath and ion-exchanged water was slowly added. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10). The product was vacuum-dried to obtain 0.219 g of a white powder calixarene compound (5).
Example 6 Production of calixarene compound (6) In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 5.00 g of the intermediate (M-3), 19.71 g of tetrahydrofuran, triphenylphosphine 5 .73 g and glycerin dimethacrylate 12.48 g were added and stirred. The inside of the flask was an ocher suspension solution. The flask was immersed in an ice bath, and 4.05 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a red transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) to obtain a pale yellow transparent liquid. After the solvent was distilled off, the residue was vacuum-dried to obtain 2.97 g of calixarene compound (6).
Example 7 Production of Calixarene Compound (7) <Production of Intermediate (M-7)>
The calixarene compound (6) (1.00 g) and dehydrated N, N-dimethylformamide (12.00 g) were placed in a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser. The flask was immersed in an ice bath and 0.181 g of sodium hydride (liquid paraffin 60 mass% dispersion) was slowly added. 7-[[(1,1-dimethylethyl) dimethylsilyl] oxy] -6-[[[(1,1-1,1-dimethylethyl) dimethylsilyl] oxy] methyl] -1-iodoheptane 2.272 g And stirred at room temperature for 20 hours. A yellow oily substance was deposited on the flask wall. Ion exchange water and 0.3N hydrochloric acid were added to adjust the pH to 6. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent: normal hexane: acetone = 95: 5), dried in vacuo, and colorless as represented by the following structural formula (h) 0.797 g of a transparent oily intermediate (M-7) was obtained.

<Production of calixarene compound (7)>
To a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 0.797 g of the intermediate (M-7) and 5.078 g of tetrahydrofuran were added. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 2.82 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The inside of the flask was a pale red transparent solution. After stirring for 24 hours, the flask was immersed in an ice bath and ion-exchanged water was slowly added. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer and extracting organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent: normal hexane: acetone = 90: 10) and dried in vacuo to give a white powder of calixarene compound (7) 0. 183 g was obtained.
Example 8 Production of Calixarene Compound (8) <Production of Intermediate (M-8)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 0.100 g of the calixarene compound (3), 1.022 g of tetrahydrofuran, 0.0930 g of triphenylphosphine, 2,2-bis (tertiary butyl) Dimethylsiloxane) propionic acid 0.1286g was added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.0717 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The flask was a colorless and transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by thin-phase chromatography (developing solvent normal hexane: acetone = 80: 20) to obtain an oily product represented by the following structural formula (i). Intermediate (M-8) 0.104g was obtained.

<Production of calixarene compound (8)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 0.104 g of the intermediate and 1.000 g of tetrahydrofuran were added. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 0.2 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The flask was a colorless and transparent solution. After stirring for 24 hours, the flask was immersed in an ice bath and ion-exchanged water was slowly added. Chloroform 10 g was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting colorless transparent liquid was purified by thin-phase chromatography (developing solvent normal hexane: acetone = 80: 20). The product was vacuum-dried to obtain 42.04 mg of calixarene compound (8) as a white powder.
Example 9 Production of calixarene compound (9) A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 2.00 g of the intermediate (M-5), 6.80 g of tetrahydrofuran, and triphenylphosphine 0. .824 g, 2-methyl-1,1 ′-(2-carboxy-2-methyl-1,3-propanediyl) ester 2-propenoic acid 0.848 g was added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.635 g of diisopropyl azodicarboxylate was slowly added dropwise. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) and dried in vacuo to obtain 1.304 g of calixarene compound (9). It was.
Example 10 Production of Calixarene Compound (10) <Production of Intermediate (M-9)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 0.500 g of the calixarene compound (9), 4.054 g of tetrahydrofuran, 0.1843 g of triphenylphosphine, 2,2-bis (tertiary butyl) Dimethylsiloxane) propionic acid 0.2549 g was added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.142 g of diisopropyl azodicarboxylate was slowly added dropwise. The flask was a colorless and transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by thin-phase chromatography (developing solvent normal hexane: acetone = 80: 20), and an oily intermediate represented by the following structural formula (j) 0.317 g of body (M-9) was obtained.

<Production of calixarene compound (10)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 0.317 g of the intermediate (M-9) and 2.000 g of tetrahydrofuran were added. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 0.5 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The flask was a colorless and transparent solution. After stirring for 24 hours, the flask was immersed in an ice bath and ion-exchanged water was slowly added. Chloroform 10 g was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 10 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting colorless transparent liquid was purified by thin phase chromatography (developing solvent normal hexane: acetone = 80: 20), dried in vacuo, and white powdered calixarene compound (10) 192. .5 mg was obtained.
Example 11 Production of Calixarene Compound (11) <Production of Intermediate (M-10)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, the intermediate (M-5) 2.00 g, tetrahydrofuran 6.80 g, triphenylphosphine 0.824 g, 2-[[(1,1 -Dimethylethyl) dimethylsilyl] oxy] -2-propenoic acid (0.663 g) was added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.635 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel and the obtained white crystal was vacuum-dried, and 2.554 g of intermediate bodies (M-10) represented by the following structural formula (k) were obtained.

<Production of calixarene compound (11)>
In a 100 mL four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.554 g of the intermediate (M-10), 50.00 g of tetrahydrofuran and 0.356 g of acetic acid were added and stirred. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 5.93 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. The flask was immersed in an ice bath and ion exchange water was added. Further, 30 g of chloroform was added, the reaction mixture was transferred to a separating funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting red transparent liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel and the obtained white crystal was vacuum-dried, and 1.551g of calixarene compounds (11) were obtained.
Example 12 Production of Calixarene Compound (12) <Production of Intermediate (M-11)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, the intermediate (M-5) 2.00 g, tetrahydrofuran 6.80 g, triphenylphosphine 0.824 g, 4-[[(1,1 -Dimethylethyl) dimethylsilyl] oxy] -2-methylenebutanoic acid 0.706 g was added and stirred. The flask is a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.635 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the obtained white crystal was vacuum-dried, and 2.420 g of intermediate bodies (M-11) represented by following Structural formula (l) were obtained.

<Production of calixarene compound (12)>
In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, the intermediate (M-11) (2.420 g), tetrahydrofuran (50.00 g), and acetic acid (0.329 g) were added and stirred. The flask was a colorless and transparent solution. The flask was immersed in an ice bath, and 5.47 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. The flask was immersed in an ice bath and ion exchange water was added. Further, 30 g of chloroform was added, the reaction mixture was transferred to a separating funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting red transparent liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. The white crystals obtained were filtered through a Kiriyama funnel and dried in vacuo to obtain 1.071 g of calixarene compound (12).
Example 13 Production of Calixarene Compound (13) <Production of Intermediate (M-12)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 5.00 g of the intermediate (M-3), 37.39 g of anhydrous acetonitrile, 7.554 g of potassium carbonate, 1-bromo-3- (2 , 2-Dimethyl-1,3-dioxane-4-yl) -2-propane (12.96 g) was added, and the mixture was stirred for 20 hours under reflux conditions. After cooling to room temperature, the pH was adjusted to 6 by adding ion exchange water and 0.3N hydrochloric acid. 50 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 50 g of chloroform to the aqueous layer and extracting organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a milky white solid. The milky white solid was dissolved in chloroform and methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the milky-white crystal obtained was vacuum-dried, and 6.61 g of intermediate bodies (M-12) represented by the following structural formula (m) were obtained.

<Production of Intermediate (M-13)>
Into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, the intermediate (M-12) 5.000 and 38.95 g of diethylene glycol monoethyl ether were added and stirred. The inside of the flask was a white suspension solution. 11.63 g of hydrazine monohydrate was added. The flask was a colorless and transparent solution. After adding 13.03 g of potassium hydroxide pellets and stirring at 100 ° C. for 30 minutes, stirring was continued for 12 hours under reflux conditions. The inside of the flask was a yellow transparent solution. The mixture was cooled to 90 ° C., 30 g of ion exchange water was added, and the mixture was stirred for 30 minutes. It cooled to room temperature, the mixed solution was moved to the beaker, and 6N hydrochloric acid was added until it became pH1. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and methanol was added to the resulting orange viscous liquid to reprecipitate the product. It filtered with the Kiriyama funnel, the milky-white crystal obtained was vacuum-dried, and 3.196 g of intermediate bodies (M-13) represented by the following structural formula (n) were obtained.

<Production of Intermediate (M-14)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.000 g of the intermediate (M-13), 0.397 g of imidazole, and 11.28 g of anhydrous methylene chloride were added and stirred. The inside of the flask was a white suspension solution. The flask was immersed in an ice bath, and 0.880 g of chlorotertiary butyldimethylsilane was slowly added dropwise over 30 minutes. It returned to room temperature and stirred for 24 hours. A sufficient amount of ion-exchanged water was added to stop the reaction, and 50 g of ethyl acetate was added to the aqueous layer to extract organic components three times. Magnesium sulfate was added to the resulting extract to dehydrate and filtered. After the solvent was distilled off, the residue was purified by column chromatography (developing solvent normal hexane: ethyl acetate = 50: 1), and a light yellow liquid intermediate (M-14) represented by the following structural formula (o) 1.577 g was obtained.

<Production of Intermediate (M-15)>
The intermediate (M-14) 1.500, triethylamine 50 g, 4-dimethylaminopyridine 0.140 g, and methylene chloride 50 g were added to a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. The flask was immersed in an ice bath and cooled to 0 ° C., and 0.479 g of methacryloyl chloride was added dropwise over 5 minutes. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 6 hours. After confirming disappearance of the starting material by ¹ H-NMR, 50 g of ion-exchanged water was added to stop the reaction. The product was extracted with 30 g of chloroform and washed with saturated brine. Magnesium sulfate was added for dehydration and filtration, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solvent: normal hexane: ethyl acetate = 19: 1), the solvent was distilled off with a rotary evaporator, and an intermediate represented by the following structural formula (p) ( M-15) 1.047 g was obtained.

<Production of calixarene compound (13)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 1.047 g of the intermediate (M-15), 35.00 g of tetrahydrofuran and 0.135 g of acetic acid were added and stirred. A clear colorless solution. The flask was immersed in an ice bath, and 2.25 ml of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was slowly added dropwise with stirring. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. The flask was immersed in an ice bath, ion-exchanged water was added, and then 30 g of chloroform was added. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting red transparent liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the obtained white crystal was vacuum-dried, and 0.5489 g of calixarene compounds (13) were obtained.
Example 14 Production of calixarene compound (14) In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, the intermediate (M-3) 7.0000), phenothiazine 0.005 g, N-methyl 100.0 g of pyrrolidone was added and stirred. The flask was immersed in an ice bath and 2.397 g of sodium hydride (liquid paraffin 60 mass% dispersion) was slowly added. 10.71 g of 2-hydroxy-3-chloropropyl methacrylate was added and stirred. The flask was heated to 90 ° C. to reflux the flask and stirred for 40 hours. The inside of the flask was a brown transparent solution. After cooling to room temperature, the flask was immersed in an ice bath, ion-exchanged water was slowly added, and further chloroform was added. The pH was adjusted to 3 by adding 1N hydrochloric acid. 30 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was removed by an evaporator, and hexane and methanol were added to the resulting orange viscous liquid to reprecipitate the product. It filtered with the Kiriyama funnel, the milky-white crystal obtained was vacuum-dried, and 4.156 g of calixarene compounds (14) were obtained.
Example 15 Production of Calixarene Compound (15) <Production of Intermediate (M-16)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 3.00 g of the intermediate (M-4), 29.24 g of tetrahydrofuran, 24.93 g of ethanol and 1.21 g of potassium hydroxide were added and refluxed. Stir for 6 hours under conditions. The inside of the flask was a white suspension. After cooling to room temperature, ion exchange water and chloroform were added. The flask was immersed in an ice bath and adjusted to pH 1 by adding 6N hydrochloric acid. 50 g of chloroform was added, the reaction mixture was transferred to a separatory funnel, and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a milky white solid. The obtained milky white crystal was vacuum-dried to obtain 2.16 g of an intermediate (M-16) represented by the following structural formula (q).

<Production of calixarene compound (15)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 1.000 g of the intermediate (M-16), 0.0560 g of tetrabutylammonium iodide, 13.55 g of 1-methoxy-2-propanol, 0.007 g of phenothiazine and 4.270 g of glycidyl methacrylate were added and stirred. The mixture was heated and stirred at 90 ° C. for 20 hours. The inside of the flask was a brown transparent solution. After cooling to room temperature, the mixed solution was transferred to a beaker, and 1N hydrochloric acid and 30 g of chloroform were added. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 30 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, and the obtained white crystal was vacuum-dried and the calixarene compound (15) 0.434g was obtained.
Example 16 Production of calixarene compound (16) A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 11.00 g of the intermediate (M-3), 72.11 g of tetrahydrofuran, triphenylphosphine 12 .62 g and 17.34 g of 4-hydroxybutyl acrylate were added and stirred. The inside of the flask was an ocher suspension solution. The flask was immersed in an ice bath, and 8.92 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a red transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. The white crystals obtained were filtered through a Kiriyama funnel and dried in vacuo to obtain 8.28 g of calixarene compound (16).
Example 17 Production of calixarene compound (17) A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 2.00 g of the intermediate (M-5), 6.80 g of tetrahydrofuran, and triphenylphosphine 0. .824g and acrylic acid 0.226g were added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.635 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) and dried in vacuo to obtain 0.627 g of calixarene compound (17). It was.
Example 18 Production of calixarene compound (18) A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 2.00 g of the intermediate (M-3), 6.80 g of tetrahydrofuran, and triphenylphosphine 0. 905.9 g and 0.398 g of hydroxyethylacrylamide were added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.698 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) and dried in vacuo to obtain 1.014 g of calixarene compound (18). It was.
Example 19 Production of calixarene compound (19) A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 2.00 g of the intermediate (M-3), 6.80 g of tetrahydrofuran, and triphenylphosphine 0. .905.9 g and 0.304 g of hydroxyethyl vinyl ether were added and stirred. The inside of the flask was a pale yellow transparent solution. The flask was immersed in an ice bath, and 0.698 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 6 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting orange viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) and vacuum dried to obtain 0.756 g of calixarene compound (19). It was.
Example 20 Production of Calixarene Compound (20) <Production of Intermediate (M-17)>
In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 8.205 g of the intermediate (1), 30.00 g of dehydrated N, N-dimethylformamide, 49% aqueous sodium hydroxide 18 .94 g was quickly charged and stirred at 300 rpm in a nitrogen flow environment. The inside of the flask became a pale yellow transparent solution. Under room temperature conditions, 28.07 g of allyl bromide was dropped over 30 minutes using a dropping funnel. Stirring was further continued after completion of the dropwise addition, and a milky white solid was precipitated after 30 minutes to form a slurry. Thereafter, the mixture was further stirred for 2 hours. Acetic acid and pure water were slowly added to stop the reaction. After filtration with a Kiriyama funnel, the resulting crystals were washed with methanol and then vacuum dried to obtain 7.75 g of an intermediate (M-17) represented by the following structural formula (r).

<Production of Intermediate (M-18)>
Into a four-necked flask equipped with a stirrer, thermometer and reflux condenser, 7.75 g of the intermediate (M-17) and 20.00 g of N, N-dimethylaniline were charged and stirred at 300 rpm in a nitrogen flow environment. did. Stirring was continued for 3 hours under reflux conditions. After cooling to room temperature, the reaction mixture was transferred to a beaker and charged with 20 g of ice and chloroform. The beaker was immersed in an ice bath, and 25.00 g of 38% concentrated hydrochloric acid was slowly added. The inside of the beaker became a pale yellow transparent solution. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 20 g of chloroform to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain a mixture of white crystals and a light green transparent liquid. Methanol was slowly added to the mixture to reprecipitate the product. After filtration with a Kiriyama funnel, the obtained white crystals were washed with methanol and then vacuum dried to obtain 7.461 g of an intermediate (M-18) represented by the following structural formula (s).

<Production of Intermediate (M-19)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 5.000 g of the intermediate (M-18) and 62.50 g of dehydrated N, N-dimethylformamide were added and stirred. The flask was immersed in an ice bath and 2.05 g of sodium hydride (liquid paraffin 60 mass% dispersion) was slowly added. 15.20 g of 1-iodododecane was added and stirred. The mixture was heated to 60 ° C. and stirred for 10 hours under reflux conditions. The inside of the flask was a brown transparent solution. After cooling to room temperature, the flask was immersed in an ice bath and ion-exchanged water was slowly added. The pH was adjusted to 3 by adding 1N hydrochloric acid. The precipitated solid was filtered and dissolved in chloroform, and methanol was added to reprecipitate the product. It filtered with the Kiriyama funnel, the milky-white crystal obtained was vacuum-dried, and 6.722 g of intermediate bodies (M-19) represented by following Structural formula (t) were obtained.

<Production of Intermediate (M-20)>
To a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 5.000 g of the intermediate (M-19), 16.88 g of methylene chloride, and 2.003 g of sodium bicarbonate were charged. Next, 3.017 g of metachloroperbenzoic acid was slowly added. Stir at room temperature for 96 hours. The inside of the flask was a yellow solution. The reaction mixture was transferred to a separatory funnel, saturated aqueous sodium hydrogen carbonate solution and chloroform were added, and the organic layer was separated. The organic layer was then washed with 10% aqueous sodium thiosulfate solution. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. After evaporating the solvent with an evaporator and dissolving in chloroform, methanol was added to recrystallize the product. The obtained orange crystals were vacuum-dried to obtain 3.351 g of an intermediate (M-20) represented by the following structural formula (u).

<Production of calixarene compound (20)>
A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 2.00 g of the intermediate (M-20), 0.0257 g of triphenylphosphine, 14.00 g of toluene, and 0.573 g of methacrylic acid. did. Stir for 6 hours under reflux conditions. After cooling to room temperature, hexane was added to the reaction solution to precipitate and remove byproducts such as triphenylphosphine. The solvent was distilled off with an evaporator, and the resulting dark brown viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10) and vacuum-dried to obtain 1.227 g of calixarene compound (20). Obtained.
Example 21 Production of Calixarene Compound (21) <Production of Intermediate (M-21)>
In a 1 L four-necked flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser, 4.50 g of sodium hydride was added under a nitrogen atmosphere, and the mineral oil was washed and removed with hexane. Subsequently, 60.00 g of dry DMF and 15.50 hexyl bromide were added, and the mixture was heated to 90 ° C. with stirring. A solution obtained by dissolving 10.00 g of the intermediate (M-1) in 30.00 g of dry DMF was added thereto using a dropping funnel, and stirring was further continued for 2 hours after the addition was completed. After cooling to room temperature, the reaction mixture was poured into ice (100 g), concentrated hydrochloric acid was added to acidify the aqueous solution, and the mixture was extracted twice with 200 g of dichloromethane. This chloroform solution was washed with water until the pH reached 5 or more, further washed with saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was removed with an evaporator to obtain a yellow liquid. Methanol was added to this mixture with stirring to precipitate a solid. This solid was collected by filtration and recrystallized from isopropyl alcohol. The obtained white crystals were vacuum-dried to obtain 15.20 g of an intermediate (M-21) represented by the following structural formula (v).

<Production of Intermediate (M-22)>
With reference to known literature (Organic & Biomolecular Chemistry, 13, 1708-1723; 2015), the intermediate structure (M-21) represented by the following structural formula (v) was used in two steps in the following structure. 12.20 g of intermediate (M-22) represented by formula (x) and 11.10 g of intermediate (M-23) represented by the following structural formula (y) were obtained.

<Production of calixarene compound (21)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.00 g of the intermediate (M-23), 1.05 g of triethylamine and 10.00 g of dichloromethane were charged and stirred. 1.36 g of lower methylmalonyl chloride was added dropwise and stirred for 7 hours. The temperature was raised to room temperature, and ion exchange water was slowly added. The pH was adjusted to 3 by adding 1N hydrochloric acid. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 20 g of dichloromethane to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, the solvent was distilled off with an evaporator, and the resulting dark brown viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10), dried in vacuo and calixarene. 1.03 g of compound (M-21) was obtained.
Example 22 Production of calixarene compound (22) <Production of calixarene compound (22)>
Into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, was charged 2.00 g of the intermediate (M-5), 7.00 g of triethylamine, and 10.00 g of dichloromethane. 9.60 g of lower methyl malonyl chloride was added dropwise and stirred for 6 hours. The temperature was raised to room temperature, and ion exchange water was slowly added. The pH was adjusted to 3 by adding 1N hydrochloric acid. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 20 g of dichloromethane to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, the solvent was distilled off with an evaporator, and the resulting dark brown viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10), dried in vacuo and calixarene. 1.17 g of compound (22) was obtained.
Example 23 Production of calixarene compound (23) <Production of calixarene compound (23)>
Into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, was charged 2.00 g of the intermediate (M-5), 7.00 g of triethylamine, and 10.00 g of dichloromethane. Then, 8.60 g of methyl chloroglyoxylate was added dropwise and stirred for 6 hours. The temperature was raised to room temperature, and ion exchange water was slowly added. The pH was adjusted to 3 by adding 1N hydrochloric acid. The reaction mixture was transferred to a separatory funnel and the organic layer was separated. The operation of adding 20 g of dichloromethane to the aqueous layer to extract organic components was performed three times, and the extract was combined with the organic layer. The organic layer was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator, the solvent was distilled off with an evaporator, and the resulting dark brown viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 90: 10), dried in vacuo and calixarene. 1.03 g of compound (22) was obtained.
Example 24 Production of Calixarene Compound (24) <Production of Calixarene Compound (24)>
In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2.00 g of the intermediate (M-5), 10.00 g of tetrahydrofuran, 1.85 g of triphenylphosphine, and 0.500 g of 2-cyanoethanol were added. Stir in. The flask is a pale yellow transparent solution. The flask was immersed in an ice bath, and 1.45 g of diisopropyl azodicarboxylate was added dropwise over 30 minutes. The inside of the flask was a pale yellow transparent solution. Stir at room temperature for 12 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The product was extracted with chloroform and washed with water and saturated brine. Magnesium sulfate was added to dehydrate and filtered. The solvent was distilled off with an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent normal hexane: acetone = 95: 5) to obtain a pale yellow transparent liquid. After the solvent was distilled off and dissolved in chloroform, methanol was added to reprecipitate the product. The white crystals obtained were filtered through a Kiriyama funnel and dried in vacuo to obtain 2.03 g of calixarene compound (24).
(Example 25) Preparation of liquid crystal composition Composition comprising a compound and a mixing ratio as shown below:

On the other hand, a composition obtained by adding 0.3% by weight of the following polymerizable compound (R-1-0) was designated as LC-1.

LC-1 nematic phase-isotropic liquid phase transition temperature (TNI) is 75 ° C., solid phase-nematic phase transition temperature (TCN) is −33 ° C., refractive index anisotropy (Δn) is 0.11, dielectric The rate anisotropy (Δε) was −2.8, and the rotational viscosity (γ1) was 98 mPa · s. Refractive index anisotropy (Δn), dielectric anisotropy (Δε), and rotational viscosity (γ1) are all measured results at 25 ° C. (the same applies hereinafter).

  Furthermore, calixarene compound (1) corresponding to compound (i)

Was added in an amount of 0.3% by weight based on 100% by weight of LC-1 to prepare a liquid crystal composition.
(Examples 26 to 45)
A liquid crystal composition was prepared in the same manner as in Example 1 except that the following compound was added to LC-1 in the addition amount shown in Table 1 instead of the 0.3 wt% calixarene compound (1). .
(Example 46)
Instead of composition LC-1, a composition comprising the following compounds and mixing ratios:

On the other hand, a liquid crystal composition was prepared in the same manner as in Example 1, except that the composition LC-2 to which 0.4 wt% of the polymerizable compound (R-1-0) was added was used.

_{T NI} is 81 ° C. of _{LC-2, T CN} is -54 ° C., [Delta] n is 0.11, [Delta] [epsilon] is -3.0, gamma ₁ was 95 MPa · s.
(Examples 47 to 69)
Instead of the calixarene compound (1) having an addition amount of 0.3% by weight in Example 25, the addition compound shown in Table 1 was added to LC-2 in the addition amount shown in Table 1, and was the same as Example 46. Thus, a liquid crystal composition was prepared.
(Comparative Example 1)
A liquid crystal composition was prepared in the same manner as in Example 1 except that the compound (P-J-1) was not used.
(Comparative Examples 2 to 14)
Instead of adding 0.3% by weight of the compound calixarene compound (1), the same manner as in Example 1 except that the following compounds were added to LC-1 or LC-2 in the addition amounts shown in Table 1. A liquid crystal composition was prepared.

The following evaluation tests were performed on the liquid crystal compositions of the examples and comparative examples. The results of each evaluation test are shown in Table 1.
(Evaluation test for low-temperature storage stability)
The liquid crystal composition was filtered with a membrane filter (manufactured by Agilent Technologies, PTFE 13 mm-0.2 μm), and left under vacuum for 15 minutes to remove dissolved air. 0.5 g of this was weighed in a vial that had been washed with acetone and sufficiently dried, and was allowed to stand in an environment at −25 ° C. for 10 days. Then, the presence or absence of precipitation was visually observed and judged in the following two stages.

  A: Precipitation cannot be confirmed.

D: Precipitation can be confirmed.
(Vertical orientation evaluation test)
An alignment having a transparent electrode layer composed of a transparent common electrode and a first substrate (common electrode substrate) having no alignment film having a color filter layer and a pixel electrode layer having a transparent pixel electrode driven by an active element A second substrate (pixel electrode substrate) having no film was produced. The liquid crystal composition was dropped onto the first substrate, sandwiched between the second substrate, and the sealing material was cured at 110 ° C. for 2 hours under normal pressure, thereby obtaining a liquid crystal cell having a cell gap of 3.2 μm. The alignment unevenness such as vertical alignment and dropping marks at this time was observed using a polarizing microscope and evaluated in the following four stages.

A: Uniform vertical alignment over the entire surface B: An acceptable level even with a slight alignment defect C: An unacceptable level with an alignment defect D: A poor alignment failure (evaluation test for pretilt angle formation)
While applying a 10 V, 100 Hz rectangular AC wave to the liquid crystal cell used in the above (vertical alignment evaluation test), UV light having an illuminance at 365 nm of 100 m / cm ² is applied for 200 seconds using a high-pressure mercury lamp. Irradiated. Thereafter, the stability of white display was evaluated by applying a physical external force to the cell while applying a rectangular AC wave of 10 V and 100 Hz, observing in a crossed Nicol state, and evaluating the following four levels.

A: Uniform orientation B: Slightly acceptable orientation defect, but acceptable level C: Orientation defect, unacceptable level D: Poor orientation failure (evaluation test of residual monomer amount)
The cell used in the above (evaluation test for pretilt angle formation) was further irradiated with a UV fluorescent lamp manufactured by Toshiba Lighting & Technology Corporation for 60 minutes (illuminance at 313 nm: 1.7 mW / cm ² ), and then the polymerizable compound (R1 The residual amount of 1-1-1) was quantified by HPLC to determine the amount of residual monomer. The evaluation was made according to the following four stages according to the residual amount of the monomer.

A: Less than 300 ppm B: 300 ppm or more and less than 500 ppm.

C: 500 ppm or more and less than 1500 ppm D: 1500 ppm or more
(Response characteristic evaluation test)
The cell having a cell gap of 3.2 μm used in the above (evaluation test for pretilt angle formation) was further irradiated with a UV fluorescent lamp manufactured by Toshiba Lighting & Technology Corporation for 60 minutes (illuminance at 313 nm: 1.7 mW / cm ² ). The response speed was measured for the cell thus obtained. The response speed was measured using a DMS703 of AUTRONIC-MELCHERS under a temperature condition of 25 ° C. at Voff at 6V. Response characteristics were evaluated in the following four stages.

A: Less than 5 ms B: 5 ms or more and less than 15 ms C: 15 ms or more and less than 25 ms D: 25 ms or more

Claims (17)

A monovalent organic group having a group represented by K ⁱ¹ in cyclophane (K ⁱ¹ represents a substituent represented by the following general formula (K-1) to general formula (K-16)) and R ¹ (R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or P ⁱ¹ —Sp ⁱ¹ —, wherein —CH ₂ — in the alkyl group represents -CH = CH-, -C≡C-, -O-, -NH-, -CO-, -COO- or -OCO- may be substituted, but -O- is not continuous) Liquid crystal composition containing one or more of the prepared compounds.

(Where
W ^K1 represents a methine group, C—CH ₃ , C—C ₂ H _5, C—C ₃ H _7, C—C ₄ H ₉ or a nitrogen atom,
W ^K2 represents a single bond, —CH ₂ —, an oxygen atom or a sulfur atom,
X ^K1 and Y ^K1 each independently represent —CH ₂ —, an oxygen atom or a sulfur atom,
Z ^K1 represents an oxygen atom or a sulfur atom,
U ^K1 , V ^K1 and S ^K1 each independently represent a methine group or a nitrogen atom, except for the combination of [U ^K1 is a methine group, V ^K1 is a methine group, and S ^K1 is a nitrogen atom]. In (K-1) to general formula (K-16), the black dot at the left end represents a bond. ) The compound is represented by the general formula (i):

(Wherein X and Y each independently represent an oxygen atom, a carbonyl group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a single bond, one in the alkylene group or two or more not adjacent to each other) —CH ₂ — may be substituted with —O—, —CO—, —COO—, —OCO— or —C (═CH ₂ ) —, and the hydrogen atom in the alkylene group is substituted with the substituent L ( L may be substituted with R ⁱⁱ¹ , R ⁱⁱ² and R ⁱⁱ³ ), but -O- is not continuous,
Z ⁱ¹ and Z ⁱ² are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO—, —CF _{2 O -, - OCF 2 -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - _{OCOC (CH 3) = CH -} , - CH 2 -CH (CH 3) COO -, - OCOCH (CH 3) -CH 2 -, - OCH 2 CH 2 O-, or an alkylene group having 2 to 20 carbon atoms In the alkylene group, one or two or more non-adjacent —CH ₂ — may be substituted with —O—, —COO— or —OCO—, and A ⁱ¹ and A ⁱ² are each independently Divalent 6-membered aromatic group, Divalent 6-membered ring heterocycle Kozokumoto, divalent 6-membered ring aliphatic group, a divalent 6-membered heterocyclic aliphatic group, a hydrogen atom is a substituent L (L of these ring structure, R ^i1, R ⁱ² and R ^It represents the same meaning as ⁱ³ .), but when there are a plurality of Z ⁱ¹ , Z ⁱ² , Z ⁱ² and A ⁱ² , they may be the same or different from each other,
R ⁱ¹ , R ⁱ² and R ⁱ³ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, K ⁱ¹ (K ⁱ¹ is a general formula (K . -1) ~ (represents a group selected from the group represented by K-16)) a group represented by or ^{P i1 -Sp} i1 - ^(P i1 represents a polymerizable group, ^{Sp i1} is or spacer group The secondary carbon atom in the alkyl group is substituted with —CH═CH—, —C≡C—, —O—, —NH—, —COO— or —OCO—. -O- is not continuous,
m ⁱ¹ and m ⁱ² represent an integer of 0 to 5;
n represents an integer of 1 to 10. )
The liquid crystal composition according to claim 1, which is a compound represented by the formula: The general formula (i) is the general formula (i-1) or the general formula (i-2).

(Wherein X, Y, A ⁱ¹ , A ⁱ² , Z ⁱ¹ , Z ⁱ² , R ⁱ¹ , R ⁱ² , R ⁱ³ , m ⁱ¹ , m ⁱ² and n are each independently X in the general formula (i) Y, A ⁱ¹ , A ⁱ² , Z ⁱ¹ , Z ⁱ² , R ⁱ¹ , R ⁱ² , R ⁱ³ , m ⁱ¹ , m ^i2, and n have the same meaning.)
The liquid crystal composition according to claim 1, which is a compound represented by the formula: One or two or more P ⁱ¹ -Sp ⁱ¹ — (P ⁱ¹ represents a group selected from the group represented by the following general formula (P-1) to general formula (P-16) ( In the formula, the black dot at the right end represents a bond.),

Sp ⁱ¹ represents an alkylene group having 1 to 20 carbon atoms or a direct bond, and one or two or more non-adjacent —CH ₂ — in the alkylene group is substituted with —O—, —COO— or —OCO—. May be. 4) The liquid crystal composition according to any one of claims 1 to 3, which comprises The compound has an alkylene group having 3 or more carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkylene group is substituted with —O—, —COO— or —OCO—. The liquid crystal composition according to any one of claims 1 to 3. The liquid crystal according to claim 4, wherein the group represented by K ⁱ¹ and P ⁱ¹ -Sp ⁱ¹ — are present by substitution of the same ring forming a cyclophane structure. Composition.   A liquid crystal composition having a negative dielectric anisotropy (Δε) containing the compound according to claim 1. General formulas (N-1), (N-2) and (N-3):

(Where
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, and one or two or more adjacent ones in the alkyl group Each of —CH ₂ — may be independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be substituted with —N═),
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be substituted with —N═. ),
And (d) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the groups (a), (b), (c) and (d) are each independently May be substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH _2. O—, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—. Represent,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or an oxygen atom,
^nN11 , ^nN12 , ^nN21 , ^nN22 , ^nN31 and ^nN32 each independently represent an integer of 0 to 3, but ^nN11 + ^nN12 , ^nN21 + ^nN22 and ^nN31 + ^nN32 are each independent. 1, 2 or 3,
When a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 are present, each may be the same as or different from each other. )
The liquid crystal composition according to claim 7, further comprising a compound selected from the group of compounds represented by: Formula (L):

(Where
R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently May be substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^L1 represents 0, 1, 2, or 3,
A ^L1 , A ^L2 and A ^L3 are each independently
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be substituted with —N═), and (c) (C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group) Alternatively, one —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be substituted with —N═. .)
The group (a), the group (b) and the group (c) are each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, — OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different from each other, and when n ^L1 is 2 or 3, and a plurality of Z ^L2 are present, They may be the same or different from each other, but exclude the compounds represented by the general formulas (N-1), (N-2) and (N-3). )
The liquid crystal composition according to claim 1, further comprising a compound represented by:   The liquid crystal composition according to claim 1, further comprising a polymerizable compound. As the polymerizable compound, the general formula (P):

(Where
Z ^p1 represents a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, or the number of carbon atoms in which the hydrogen atom may be substituted with a halogen atom. An alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and an alkenyloxy group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom Represents the group or -Sp ^p2 -R ^p2 ,
R ^p1 and R ^p2 are the following formulas (R-I) to (R-IX):

(Where
* Binds to Sp ^p1 ,
R ^{2 to} R ⁶ 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,
W represents a single bond, —O— or a methylene group,
T represents a single bond or —COO—;
p, t, and q each independently represents 0, 1, or 2. )
Represents one of the following:
Sp ^p1 and Sp ^p2 represent spacer groups,
L ^p1 and L ^p2 each independently represent 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 ^a —, —NR ^a —CO—, —SCH ₂ —, —CH ₂ S ^{-, - CH = CR a -COO} -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - COO-CR a = CH-COO -, - ^{COO-CR a = CH-OCO} -, - OCO-CR a = CH-COO -, - OCO-CR a = CH-OCO -, - (CH 2) z -C (= O) -O -, - ( _{CH 2) z -O- (C =} O) -, - O- (C = O) - (CH 2) z -, - (C = O _{-O- (CH 2) z -,} - CH 2 (CH 3) C-C (= O) -O -, - CH 2 (CH 3) C-O- (C = O) -, - O- ( C═O) —C (CH ₃ ) CH ₂ , — (C═O) —O—C (CH ₃ ) —CH 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 ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and z represents an integer of 1 to 4).
M ^p2 represents 1,4-phenylene group, 1,4-cyclohexylene group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2, 5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5 -Represents a diyl group or a single bond, but M ^p2 is unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms , ^May be substituted with a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a nitro group or —R ^p1 ,
M ^p1 represents the following formulas (i-11) to (ix-11):

(In the formula, * binds to Sp ^p1 and ** binds to L ^p1 , L ^p2 or Z ^p1 .)
Any hydrogen atom on M ^p1 represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or the number of carbon atoms 1-12 halogenated alkoxy groups, halogen atoms, cyano groups, nitro groups or -R ^p1 may be substituted,
M ^p3 represents the following formulas (i-13) to (ix-13):

(In the formula, * binds to Z ^p1 and ** binds to L ^p2 .)
Any hydrogen atom on M ^p3 represents an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or the number of carbon atoms 1-12 halogenated alkoxy groups, halogen atoms, cyano groups, nitro groups or -R ^p1 may be substituted,
m ^{p2 to} m ^p4 each independently represents 0, 1, 2, or 3,
m ^p1 and m ^p5 each independently represent 1, 2 or 3;
When a plurality of Z ^p1 are present, they may be the same as or different from each other. When a plurality of R ^p1 are present, they may be the same as or different from each other, and a plurality of R ^p2 are present. When present, they may be the same as or different from each other. When a plurality of Sp ^p1 are present, they may be the same as or different from each other. When there are a plurality of Sp ^{p2 May} be the same or different from each other, and when a plurality of L ^p1 are present, they may be the same or different from each other, and when a plurality of M ^p2 are present, they are They may be the same or different. )
The liquid crystal composition according to claim 10, comprising one or more compounds represented by the formula:   A liquid crystal display element comprising two substrates and a liquid crystal layer using the liquid crystal composition according to any one of claims 1 to 11 provided between the two substrates.   A liquid crystal layer using the liquid crystal composition according to any one of claims 4 to 12 provided between the two substrates and the two substrates, wherein the liquid crystal layer is a polymer of a cyclophane compound. A liquid crystal display element having   The liquid crystal display element according to claim 12, which is for active matrix driving.   The liquid crystal display element according to claim 12, which is a PSA type, a PSVA type, a VA type, an IPS type, an FFS type, or an ECB type.   The liquid crystal display element according to claim 12, wherein at least one of the two substrates does not have an alignment film. General formula (ii)

(Wherein X and Y represent an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms or a single bond, and one or two or more non-adjacent —CH ₂ — in the alkylene group are —O—. , —CO—, ^—COO— , ^—OCO— , or —C (═CH ₂ ) —, and the hydrogen atom in the alkylene group is substituted with the substituent L (L is R ⁱⁱ¹ , R ⁱⁱ² and The same meaning as R ⁱⁱ³ ) may be substituted.
Z ⁱ¹ and Z ⁱ² are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —OOCO—, —CF _{2 O -, - OCF 2 -} , - CH = CHCOO -, - OCOCH = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - _{OCOC (CH 3) = CH -} , - CH 2 -CH (CH 3) COO -, - OCOCH (CH 3) -CH 2 -, - OCH 2 CH 2 O-, or an alkylene group having 2 to 20 carbon atoms In the alkylene group, one or two or more non-adjacent —CH ₂ — may be substituted with —O—, —COO— or —OCO—, and A ⁱⁱ¹ and A ⁱⁱ² are each independently Divalent 6-membered aromatic group, Divalent 6-membered ring Containing aromatic group, a divalent 6-membered ring aliphatic group, a divalent 6-membered heterocyclic aliphatic group, a hydrogen atom of these ring structure substituent L (L is, R ^ii1, R ⁱⁱ² and R ⁱⁱ³ represents the same meaning.) ^May be substituted, but when there are a plurality of Z ⁱⁱ¹ , Z ⁱⁱ² , Z ⁱⁱ² and A ⁱⁱ² , they may be the same or different from each other,
R ⁱⁱ¹ , R ⁱⁱ² and R ⁱⁱ³ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or a group represented by K ^i1. In the alkyl group, —CH ₂ — may be substituted with —CH═CH—, —C≡C—, —O—, —NH—, —COO— or —OCO—, but —O— is continuously present. Should not
m ⁱ¹ and m ⁱ² represent an integer of 0 to 5;
n contains 1 type, or 2 or more types of the compound represented by the integer of 1-10. )
A compound represented by

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