JP2008297210A - Spiro compound, liquid crystal composition and liquid crystal display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having good compatibility with a nematic liquid crystal, and contributing to the enlargement of the temperature range exhibiting a nematic phase. <P>SOLUTION: The compound is represented by general formula (I) (wherein, A<SP>1</SP>and A<SP>2</SP>are each independently a substitutive or non-substitutive 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl; ring B<SP>1</SP>and ring B<SP>2</SP>are each a spiro ring which may contain an oxygen atom or a sulfur atom; X is a divalent group including a carbonate group; L<SP>1</SP>, L<SP>2</SP>and L<SP>3</SP>are each independently a single bond or a prescribed divalent group; R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, a halogen atom or a 1-20C substitutive or non-substitutive alkyl group; and n and m are each an integer of 0-2). The liquid crystal composition contains at least one kind of the compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a compound having a spiro skeleton, a liquid crystal composition containing the compound, and a liquid crystal display device using the liquid crystal composition. In particular, the present invention relates to a compound useful for preparing a nematic liquid crystal composition used for various liquid crystal elements.

  Liquid crystal display elements are widely used in calculators, watches, mobile phones, household electrical appliances, measuring instruments, electronic notebooks, in-train monitors, printers, computers, televisions, and the like. Typical liquid crystal display methods include a TN (twisted nematic) method, an STN (super twisted nematic) method, a GH (guest host) method, an IPS (in-plane switching) method, a VA (vertical alignment B) method, and a C alignment method. An (optically compensated bend) method can be used.

  These display methods are all display methods that utilize changes in light transmission, reflection, absorption, and the like due to voltage driving of the nematic liquid crystal composition. Therefore, a nematic liquid crystal composition for driving has been extensively researched and developed from the viewpoint of various physical properties including the temperature range of liquid crystal phase, viscosity, birefringence, dielectric anisotropy, and elastic constant.

  Usually, a nematic liquid crystal composition is prepared by mixing many compounds. Conditions required for each compound include the optimum physical properties for each mode, such as chemical stability to water and air, viscosity, dielectric anisotropy, birefringence, and a wide liquid crystal phase temperature range, and other compounds. And compatibility. In particular, paying attention to compatibility, in recent years, liquid crystal display elements have been used under harsh conditions such as automobiles and outdoors, so highly compatible compounds are strongly demanded to prevent precipitation of compounds at low temperatures. It has been. In general, in order to increase the upper limit temperature of the nematic phase of the liquid crystal composition, a compound having a high clearing point (referred to as Iso point) is mixed, so that the Iso point is high and compatibility with the nematic liquid crystal composition is achieved. There is a need for compounds having a high value.

  On the other hand, with the widespread use of digital information, the importance of displays for displaying digital information (hereinafter referred to as electronic paper) is increasing. The performance required for electronic paper includes high visibility and low power consumption. High visibility means a white background close to paper. For this purpose, a display method based on a scattered white background similar to paper is suitable. Regarding the low power consumption, the reflective display method has lower power consumption than the self-luminous display method. Until now, many methods have been proposed as electronic paper. For example, a reflective liquid crystal display method, an electrophoretic display method, a magnetophoretic display method, a dichroic rotation method, an electrochromic display method, a leucothermal display method, and the like. Both methods are not satisfactory from the viewpoint of high visibility, and their improvement has been demanded.

Many types of liquid crystal elements (liquid crystal display elements) have already been proposed. Among them, GH (guest host) type liquid crystal elements are capable of bright display and are expected as liquid crystal elements suitable for a reflective type. ing. The guest host method is a display method using a liquid crystal composition in which a dichroic dye is dissolved as a guest in a nematic liquid crystal which is a host. The dichroic dye has a uniaxial light absorption axis and absorbs only light that vibrates in the direction of the light absorption axis. Therefore, the orientation of the dichroic dye is changed in accordance with the movement of the liquid crystal due to the electric field, The light absorption state of the cell can be changed by controlling the direction of the light absorption axis.
Further, as a method for absorbing light in all directions, a phase transition type guest host method using a chiral nematic phase in combination with a chiral agent has been proposed (see Non-Patent Document 1). This method enables bright display without using a polarizing plate (see Patent Document 1).

It is known that one factor that affects the display contrast of a guest host (GH) type liquid crystal element is the order parameter (also referred to as S value) of the dichroic dye in the liquid crystal composition constituting the liquid crystal layer. Accordingly, in order to improve the display characteristics of the GH liquid crystal display element, it is important to provide a nematic liquid crystal composition in which the dichroic dye exhibits higher order parameters. In addition, since it is used in various environments, it is desired to provide a liquid crystal composition exhibiting a nematic phase in a wider temperature range.
D. L. White; N. Taylor; Appl. Phys. , Vol. 45, 4718 (1974) JP 2006-83338 A

An object of the present invention is to provide a compound that has good compatibility with a nematic liquid crystal and contributes to expansion of a temperature range showing a nematic phase.
Another object of the present invention is to provide a liquid crystal composition that has a wide temperature range exhibiting a nematic phase and contributes to improvement of the order parameter of the dichroic dye.
Furthermore, an object of the present invention is to provide a liquid crystal element having a high display contrast using the liquid crystal composition, particularly a phase transition type guest-host type liquid crystal element.

式中、Ａ¹及びＡ²は各々独立に、置換もしくは無置換の、１，４−シクロへキシレン、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ピラジン−２，５−ジイル又はピリダジン−３，６−ジイルを表わし；
スピロ環を構成する環Ｂ¹及び環Ｂ²は各々独立に、

を表し（＊は連結部位を表す）、Ｙ¹及びＹ²は各々独立に、−ＣＨ₂−、酸素原子、又は硫黄原子を表し；
Ｘは、下記基

を含む二価基を表わし、Ｚ¹、Ｚ²及びＺ³は各々独立に、酸素原子又は硫黄原子を表わし；
Ｌ¹、Ｌ²及びＬ³は各々独立に単結合、−ＣＨ₂−、酸素原子、硫黄原子、−ＮＲ³−（Ｒ³は水素原子又は炭素数１〜３のアルキル基を表す）、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ³−、−ＮＲ³−ＣＯ−、−ＣＨ₂ＣＨ₂−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ₂−ＯＣＯ−、−ＣＯＯ−ＣＨ₂−、−ＯＣＯＯ−ＣＨ₂−、−ＣＨ₂−ＯＣＯＯ−又は−ＣＨ₂−ＯＣＯＯ−ＣＨ₂−を表し；
Ｒ¹及びＲ²は各々独立に、水素原子、ハロゲン原子、又は炭素数１〜２０の置換もしくは無置換アルキル基を表し、アルキル基を構成するＣＨ₂基のうち１つもしくは隣接していない２つ以上のＣＨ₂基は、酸素原子もしくは硫黄原子で置換されていてもよく；
ｎ及びｍはそれぞれ、０〜２の整数を表わす。 Means for solving the above problems are as follows.
[1] Compound represented by the following general formula (I):

In the formula, A ¹ and A ² are each independently substituted or unsubstituted 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5. -Represents diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl;
Ring B ¹ and Ring B ² constituting the spiro ring are each independently

(* Represents a linking site), Y ¹ and Y ² each independently represent —CH ₂ —, an oxygen atom, or a sulfur atom;
X is the following group

And Z ¹ , Z ² and Z ³ each independently represents an oxygen atom or a sulfur atom;
L ¹ , L ² and L ³ are each independently a single bond, —CH ₂ —, an oxygen atom, a sulfur atom, —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), — CO -, - COO -, - OCO -, - OCOO -, - CO-NR 3 -, - NR 3 -CO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CH 2 _{S -, - SCH 2 -,} - CH = CH -, - C≡C -, - CH 2 -OCO -, - COO-CH 2 -, - OCOO-CH 2 -, - CH 2 -OCOO- or -CH ₂ represents —OCOO—CH ₂ —;
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and one of CH ₂ groups constituting the alkyl group or not adjacent 2 One or more CH ₂ groups may be substituted with oxygen or sulfur atoms;
n and m each represents an integer of 0 to 2.

のいずれかであることを特徴とする［１］の化合物。
［３］ 前記一般式（Ｉ）中、Ｘが−ＯＣＯＯ−であること特徴とする［１］又は［２］の化合物。
［４］ 前記一般式（Ｉ）中、ｍ＋ｎが２以上であることを特徴とする［１］〜［３］のいずれかの化合物。
［５］ 液晶化合物であることを特徴とする［１］〜［４］のいずれかの化合物。
［６］ ［１］〜［５］のいずれかの化合物の少なくとも１種を含有することを特徴とする液晶組成物。
［７］ 少なくとも１種のカイラル剤をさらに含有することを特徴とする［６］の液晶組成物。
［８］ 少なくとも１種の二色性色素をさらに含有することを特徴とする［６］又は［７］の液晶組成物。
［９］ 少なくとも一方が透明電極である一対の電極間に液晶層を有する液晶素子であって、該液晶層が、［６］〜［８］のいずれかの液晶組成物を含有する液晶素子。
［１０］ 少なくとも一方が透明電極である一対の電極間に高分子媒体層を有する液晶素子であって、該高分子媒体層が、高分子と該高分子中に分散された［６］〜［８］のいずれかの液晶組成物とを含む液晶素子。
［１１］ 少なくとも一方が透明電極である一対の電極間に液晶層を有する液晶素子であって、該液晶層が、［６］〜［８］のいずれかの液晶組成物を含むマイクロカプセルを含有する液晶素子。 [2] Spiro ring in the general formula (I)

[1] The compound of [1].
[3] The compound of [1] or [2], wherein in the general formula (I), X is —OCOO—.
[4] The compound according to any one of [1] to [3], wherein in the general formula (I), m + n is 2 or more.
[5] The compound according to any one of [1] to [4], which is a liquid crystal compound.
[6] A liquid crystal composition comprising at least one compound of any one of [1] to [5].
[7] The liquid crystal composition according to [6], further comprising at least one chiral agent.
[8] The liquid crystal composition according to [6] or [7], further comprising at least one dichroic dye.
[9] A liquid crystal element having a liquid crystal layer between a pair of electrodes, at least one of which is a transparent electrode, wherein the liquid crystal layer contains the liquid crystal composition according to any one of [6] to [8].
[10] A liquid crystal device having a polymer medium layer between a pair of electrodes, at least one of which is a transparent electrode, wherein the polymer medium layer is dispersed in a polymer and the polymer. And a liquid crystal composition according to any one of 8).
[11] A liquid crystal element having a liquid crystal layer between a pair of electrodes, at least one of which is a transparent electrode, the liquid crystal layer containing a microcapsule containing the liquid crystal composition according to any one of [6] to [8] Liquid crystal element.

ADVANTAGE OF THE INVENTION According to this invention, the compatibility with a nematic liquid crystal is good and the compound which contributes to expansion of the temperature range of a nematic phase can be provided.
In addition, according to the present invention, it is possible to provide a liquid crystal composition that has a wide temperature range of the nematic phase and contributes to an improvement in the order parameter of the dichroic dye.
Furthermore, according to the present invention, it is possible to provide a liquid crystal element using the liquid crystal composition and having a high display contrast, in particular, a phase transition guest-host type liquid crystal element.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. In the present specification, “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.
The present invention relates to a liquid crystal compound having both a spiro skeleton and a carbonic acid ester group (or a group in which some or all of oxygen atoms in the carbonic acid ester group are replaced with sulfur atoms). Due to its structural characteristics, the compound of the present invention is characterized by a high Iso point and a high maximum temperature of the nematic phase when it is a compound that alone becomes a nematic phase. Regardless of the presence or absence of liquid crystallinity, it has good compatibility with nematic liquid crystals, and by adding to nematic liquid crystals, the temperature range of the nematic phase can be expanded.
Further, when the dichroic dye is dissolved in the liquid crystal composition containing the compound of the present invention, the order parameter (S value) of the dye is improved. That is, a GH mode, particularly a phase transition type GH mode liquid crystal element using a liquid crystal composition containing the compound of the present invention can realize a high display contrast.

Hereinafter, various materials used in the present invention will be described.
[Compound represented by formula (I)]

In the formula, A ¹ and A ² are each independently substituted or unsubstituted 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5. -Represents diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl.

Ring B ¹ and ring B ² constituting the spiro ring each independently represent the following ring.

In addition, * in a formula represents a connection part. Y ¹ and Y ² each independently represent —CH ₂ —, an oxygen atom, or a sulfur atom.

  In said formula (I), X represents the bivalent group containing the following group.

In the above formula, Z ¹ , Z ² and Z ³ each independently represent an oxygen atom or a sulfur atom.
That is, X is a divalent group including a carbonic acid ester group or a group in which some or all of the oxygen atoms in the carbonic acid ester group are substituted with sulfur atoms (hereinafter collectively referred to as “carbonic acid ester group etc.”). X may contain an alkylene group together with a carbonate group or the like. Examples of X include the following groups.

X is preferably contains a carbonic ester group, specifically, -OCOO -, - OCOO-CH 2 -, - CH 2 -OCOO- or -CH ₂ -OCOO-CH ₂ - is preferably Particularly preferred is a carbonate group, i.e. -OCOO-.

In the above formula (I), L ¹ , L ² and L ³ are each independently a single bond, —CH ₂ —, an oxygen atom, a sulfur atom, —NR ³ — (R ³ is a hydrogen atom or having 1 to 3 carbon atoms. Represents an alkyl group), —CO—, —COO—, —OCO—, —OCOO—, —CO—NR ³ —, —NR ³ —CO—, —CH ₂ CH ₂ —, —CH ₂ O—, — _{OCH 2 -, - CH 2 S} -, - SCH 2 -, - CH = CH -, - C≡C -, - CH 2 -OCO -, - COO-CH 2 -, - OCOO-CH 2 -, - CH ₂ —OCOO— or —CH ₂ —OCOO—CH ₂ — is represented.

In the formula (I), R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and 1 of CH ₂ groups constituting the alkyl group. Two or more CH ₂ groups which are not adjacent to each other may be substituted with an oxygen atom or a sulfur atom.
In the formula (I), n and m each represents an integer of 0 to 2.

In the general formula (I), A ¹ and A ² are each independently substituted or unsubstituted 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine. -2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, n- Propyl group, isopropyl group, tert-butyl group), alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, n-propoxy group, tert -Butoxy group) and a cyano group, preferably a halogen atom, an alkyl group or an alkoxy group, and more preferably a halogen atom or an alkyl group.

A ¹ and A ² are preferably each independently substituted or unsubstituted 1,4-trans-cyclohexylene or 1,3-dioxane-2,5-diyl, more preferably substituted or unsubstituted. Substituted 1,4-trans-cyclohexylene.
A ¹ and A ² are more preferably each independently unsubstituted 1,4-trans-cyclohexylene, or 1,3-dioxane-2,5-diyl, most preferably unsubstituted. 1,4-trans-cyclohexylene.
In addition, when there are a plurality of A ¹ and A ² , they may be the same or different.

In the general formula (I), L ¹ , L ² and L ³ are each independently a single bond, —CH ₂ —, an oxygen atom, a sulfur atom, —NR ³ — (R ³ is a hydrogen atom or a carbon number of 1 to 3 represents an alkyl group), —CO—, —COO—, —OCO—, —OCOO—, —CO—NR ³ —, —NR ³ —CO—, —CH ₂ CH ₂ —, —CH ₂ O—. _{, -OCH 2 -, - CH 2} S -, - SCH 2 -, - CH = CH -, - C≡C -, - CH 2 -OCO -, - COO-CH 2 -, - OCOO-CH 2 -, —CH ₂ —OCOO— or —CH ₂ —OCOO—CH ₂ —, and more preferably a single bond, —COO—, —OCO—, —OCOO—, —CO—NR ³ —, —NR ³ —CO _{-, - CH 2 CH 2 -} , - CH 2 O -, - OCH 2 -, - CH 2 -OCO- or -COO-CH ₂ - represents a further good Details, each independently, a single bond, -COO -, - OCO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CH 2 -OCO- or -COO-CH ₂ - and To express. Further, when there are a plurality of L ¹ , L ² and L ³ , they may be the same or different.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and one of CH ₂ groups constituting the alkyl group. Two or more CH ₂ groups which are not adjacent to each other may be substituted with an oxygen atom or a sulfur atom. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, n- Propyl group, isopropyl group, tert-butyl group), alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, n-propoxy group, tert -Butoxy group) and a cyano group, preferably a halogen atom, an alkyl group or an alkoxy group, and more preferably a halogen atom or an alkyl group.

R ¹ and R ² preferably each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 8 carbon atoms). One of the constituent CH ₂ groups or two or more non-adjacent CH ₂ groups may be substituted with an oxygen atom or a sulfur atom. The substituent is the same as described in the previous paragraph.
R ¹ and R ² more preferably represent an unsubstituted alkyl group having 1 to 20 carbon atoms, and ^one of CH ₂ groups constituting the alkyl group or two or more adjacent CH ₂ groups are It may be substituted with an oxygen atom.
R ¹ and R ² most preferably represent an unsubstituted alkyl group having 1 to 20 carbon atoms.

In general formula (I), spiro ring moiety

  In the general formula (I), n and m each independently represent an integer of 0 to 2, preferably n + m2 or more, more preferably n + m is 2 or 3, most preferably n = 2, and m = 0.

  Specific examples of the compound represented by formula (I) are shown below, but are not limited to the following specific examples. Regarding the following compound, it is shown as an exemplified compound (X) by the numbers in the arc ().

  The compound represented by the general formula (I) can be synthesized by combining known methods. For example, “Tetrahedron” (1989); 45 (3); p.687-694. , "Liebigs. Ann." (1995), p1319-1326.

  The compound represented by the general formula (I) may have liquid crystallinity or may not have liquid crystallinity.

[Liquid crystal composition]
The present invention relates to a liquid crystal composition containing at least one compound represented by the general formula (I). The liquid crystal composition of the present invention is useful for production of a liquid crystal element, particularly a guest-host type liquid crystal display element. The liquid crystal composition of the present invention can be nematic in a wide temperature range by containing the compound represented by the general formula (I). By dissolving the dichroic dye, the order parameter of the dichroic dye can be improved, and when used for manufacturing a GH liquid crystal display element, it can contribute to an improvement in display contrast.

  In the liquid crystal composition of the present invention, only one kind of the compound represented by the general formula (I) may be contained, or plural kinds may be contained. The content of the compound represented by the general formula (I) in the liquid crystal composition is not particularly limited, and the preferred range varies depending on the role, function, etc. of the compound in the composition. The composition of the host liquid crystal necessary for the desired display contrast may be determined by measuring the refractive index anisotropy Δn of the prepared host liquid crystal, the dye solubility, and the order parameter of the dye.

(Dichroic dye)
The liquid crystal composition of the present invention may further contain at least one dichroic dye. A dichroic dye is defined as a compound that dissolves in a host liquid crystal and has a function of absorbing light. It is preferable that the dichroic dye has a large dichroic ratio (R) and order parameter (S) and exhibits good compatibility with the host liquid crystal. The dichroic dye may have any absorption maximum and absorption band, but preferably has an absorption maximum in the yellow region (Y), magenta region (M), or cyan region (C). . Moreover, although the dichroic dye used for the liquid crystal element of this invention may be used independently, what mixed two or more may be used. When mixing a plurality of dyes, it is preferable to use a mixture of dichroic dyes having absorption maxima in Y, M, and C. Known dichroic dyes include, for example, A.I. V. Examples include those described by Ivashchenko, Diachronic Dies for Liquid Crystal Display, CRC, 1994. A method for performing full color display by mixing a yellow dye, a magenta dye and a cyan dye is detailed in “Color Chemistry” (written by Sumio Tokita, Maruzen, 1982). Here, the yellow region is a range of 430 to 490 nm, the magenta region is a range of 500 to 580 nm, and the cyan region is a range of 600 to 700 nm.

  The chromophore of the dichroic dye may be any, for example, azo dye, anthraquinone dye, perylene dye, merocyanine dye, azomethine dye, phthaloperylene dye, indigo dye, azulene dye, dioxazine dye, polythiophene dye, Examples include phenoxazine dyes. Preferred are azo dyes, anthraquinone dyes, and phenoxazine dyes, and particularly preferred are anthraquinone dyes and phenoxazone dyes (phenoxazin-3-one).

The azo dye may be any of a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a pentakisazo dye, and is preferably a monoazo dye, a bisazo dye, or a trisazo dye.
The ring structure contained in the azo dye includes aromatic groups (benzene ring, naphthalene ring, etc.) as well as heterocyclic rings (quinoline ring, pyridine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, imidazole ring, Benzimidazole ring, pyrimidine ring, etc.).

  As the substituent of the anthraquinone dye, those containing an oxygen atom, a sulfur atom or a nitrogen atom are preferable, and examples thereof include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group and an arylamino group. The substitution number of the substituent may be any number, but di-substitution, tri-substitution, and tetrakis substitution are preferred, and di-substitution and tri-substitution are particularly preferred. The substitution position of the substituent may be any place, but preferably 1,4-position disubstitution, 1,5-position disubstitution, 1,4,5-position trisubstitution, 1,2,4-position trisubstitution, They are 1,2,5-trisubstituted, 1,2,4,5-tetrasubstituted, 1,2,5,6-tetrasubstituted structures.

  The substituent of the phenoxazone dye (phenoxazin-3-one) preferably includes an oxygen atom, a sulfur atom or a nitrogen atom, and examples thereof include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group and an arylamino group.

  Specific examples of the dichroic dye that can be used in the present invention are shown below, but the present invention is not limited to the following specific examples.

  Specific examples of the azo dichroic dye that can be used in the present invention are shown below, but the present invention is not limited to the following specific examples.

  Specific examples of dioxazine dichroic dyes and merocyanine dichroic dyes that can be used in the present invention are shown below, but the present invention is not limited to the following specific examples.

  In the liquid crystal composition of the present invention, the content of the dichroic dye is not limited, but the content of the dichroic dye (in the case of a mixture, the total content of the dichroic dye) is The content (when the compound represented by the formula (I) is a host liquid crystal, the content of the compound) is preferably 0.1 to 15% by mass, and 0.5 to 6% by mass. It is particularly preferred. It is also desirable to determine the dye concentration necessary for the desired optical density by measuring the absorption spectrum of the liquid crystal cell.

(Host LCD)
The liquid crystal composition of the present invention preferably contains a liquid crystal. The liquid crystal is preferably a liquid crystal having a function of changing the alignment state by the action of an electric field and controlling the alignment state of the dichroic dye dissolved as a guest, that is, a liquid crystal functioning as a guest liquid crystal. . When the compound represented by the general formula (I) can function as a guest liquid crystal alone, it is not necessary to add a liquid crystal separately.

  The host liquid crystal is preferably a liquid crystal exhibiting a nematic phase. The host liquid crystal is preferably a mixture of at least one compound represented by the general formula (I) and a known liquid crystal compound. The absolute value of the refractive index anisotropy (Δn) of the host liquid crystal is preferably 0.25 or less. More preferably, | Δn | <0.15, still more preferably | Δn | <0.10, and even more preferably | Δn | <0.05.

Specific examples of known liquid crystal compounds include azomethine compounds, cyanobiphenyl compounds, cyanophenyl esters, fluorine-substituted phenyl esters, cyclohexanecarboxylic acid phenyl esters, fluorine-substituted cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexane, fluorine-substituted phenylcyclohexane, cyano. Examples thereof include substituted phenylpyrimidine, fluorine-substituted phenylpyrimidine, alkoxy-substituted phenylpyrimidine, fluorine-substituted alkoxy-substituted phenylpyrimidine, phenyldioxane, tolan compounds, fluorine-substituted tolan compounds, alkenylcyclohexylbenzonitrile, and the like. The liquid crystal compounds described on pages 154 to 192 and pages 715 to 722 of “Liquid Crystal Device Handbook” (Japan Society for the Promotion of Science 142nd edition, Nikkan Kogyo Shimbun, 1989) can be used. It is also possible to use a fluorine-substituted host liquid crystal suitable for TFT driving. For example, Merck's liquid crystal (ZLI-4692, MLC-6267, 6284, 6287, 6288, 6406, 6422, 6423, 6425, 6435, 6437, 7700, 7800, 9000, 9100, 9200, 9300, 10000, etc. Product name) and Chisso Corporation liquid crystals (LIXON 5036xx, 5037xx, 5039xx, 5040xx, 5041xx, etc., all of which are trade names).
The host liquid crystal used in the present invention may have a positive or negative dielectric anisotropy.

(Chiral agent)
Further, a chiral agent may be added to the liquid crystal composition of the present invention. By adding a chiral agent, it is more suitable as a material for a phase transition type guest-host type liquid crystal element. The chiral agent means an optically active substance that, when added to the host liquid crystal material, causes the liquid crystal composition to exhibit a chiral nematic phase. For example, the chiral agents for TN and STN described in Japan Society for the Promotion of Science 142nd Committee, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, pages 199 to 202 are mentioned.

In the liquid crystal composition of the present invention, the content of the chiral agent is not limited, but when the cell gap of the liquid crystal cell used as the liquid crystal element of the present invention is d and the helical pitch of the liquid crystal is P, 0.1 ≦ d It is preferable to contain so that it may become / P <= 20. More preferably, 0.25 ≦ d / P ≦ 5, still more preferably 0.4 ≦ d / P ≦ 2, and still more preferably 0.5 ≦ d / P ≦ 1.
The helical pitch is defined as the distance that the helical structure of liquid crystal molecules turns 360 °.

(Other additives)
The liquid crystal composition of the present invention contains a compound that does not exhibit liquid crystallinity for the purpose of changing the physical properties of the host liquid crystal to a desired range (for example, for the purpose of setting the temperature range of the liquid crystal phase to a desired range). May be added. Moreover, you may contain compounds, such as a ultraviolet absorber and antioxidant.

  The method for preparing the liquid crystal composition of the present invention is not particularly limited, and the liquid crystal composition can be prepared by mixing each component by a commonly used means. The dichroic dye is preferably dissolved in the host liquid crystal. Dissolution of the dichroic dye in the host liquid crystal can utilize mechanical stirring, heating, ultrasonic waves, or a combination thereof.

[Liquid crystal element]
The liquid crystal element of the present invention is a liquid crystal element provided with a liquid crystal layer containing the liquid crystal composition of the present invention. The liquid crystal element of the present invention includes, for example, a liquid crystal layer containing the liquid crystal composition of the present invention sandwiched between a pair of electrode substrates (at least one of which is preferably a transparent electrode substrate) and sandwiched between the pair of electrode substrates. Can be configured. As the substrate, a glass or plastic substrate is usually used, and examples of the plastic substrate include acrylic resin, polycarbonate resin, and epoxy resin. The substrate is detailed in, for example, the Japan Society for the Promotion of Science 142nd edition, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, pages 218-231. An electrode layer is formed on the substrate, preferably a transparent electrode. As the electrode layer, indium oxide, indium tin oxide (ITO), tin oxide, or the like is used. As the transparent electrode, for example, those described in Japan Society for the Promotion of Science 142nd Committee, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, pp. 232-239 are used.

In the liquid crystal element of the present invention, for the purpose of aligning liquid crystal, it is preferable to form a layer subjected to alignment treatment on the surface where the liquid crystal and the substrate are in contact. Examples of the alignment treatment include a method of applying and aligning a quaternary ammonium salt, a method of applying polyimide and aligning by rubbing, a method of aligning and depositing SiO _x from an oblique direction, and photoisomerization. Examples include an alignment method using light irradiation. As for the alignment film, for example, those described in Japan Society for the Promotion of Science 142nd Committee, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, pages 240 to 256 are used.

  The liquid crystal element of the present invention can be produced by providing the substrates with a space of 1 to 50 μm through a spacer and injecting the liquid crystal composition of the present invention into the space. As the spacer, for example, those described in the 142nd Committee of the Japan Society for the Promotion of Science, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, pages 257 to 262 are used. The liquid crystal composition of the present invention can be disposed in a space between substrates by coating or printing on the substrates.

  The liquid crystal element of the present invention can be driven by a simple matrix driving method or an active matrix driving method using a thin film transistor (TFT). The driving method is described in detail, for example, on pages 387 to 460 of “Liquid Crystal Device Handbook” (edited by the 142th Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989). Available as

  The liquid crystal display using the liquid crystal element of the present invention may be of any type. For example, (1) Homogeneous orientation, (2) Homeotropic, described in the guest host system described in Japan Society for the Promotion of Science 142nd Committee, “Liquid Crystal Device Handbook”, Nikkan Kogyo Shimbun, 1989, page 309 (3) focal conic alignment and (4) homeotropic alignment, (5) combination with Super Twisted Nematic (STN), (6) with ferroelectric liquid crystal (FLC) Combination, also described by Tatsuo Uchida, “Reflective color LCD integrated technology”, CMMC, 1999, Chapter 2-1 (GH mode reflective color LCD), pages 15 to 16, (1) Heilmeier type GH mode, (2) 1/4 wavelength plate type GH mode, (3) Two-layer type GH mode, (4) Phase transition Type GH mode, and (5) polymer dispersed liquid crystal (PDLC) type GH mode.

Furthermore, the liquid crystal element of the present invention is disclosed in JP-A-10-67990, JP-A-10-239702, JP-A-10-133223, JP-A-10-339881, JP-A-11-52411, JP-A-11-64880, JP-A-2000-. It can be used for the stacked GH mode described in, for example, No. 221538.
The liquid crystal element of the present invention can be used for a GH mode using microcapsules described in JP-A-11-24090. That is, one embodiment of the liquid crystal element of the present invention has a liquid crystal layer between a pair of electrodes, at least one of which is a transparent electrode, and the liquid crystal layer contains a microcapsule containing the liquid crystal composition of the present invention. This is a GH mode liquid crystal element using a capsule.
Further, the liquid crystal element of the present invention is disclosed in JP-A-5-61025, JP-A-5-265053, JP-A-6-3691, JP-A-6-23061, JP-A-5-203940, JP-A-6-242423, and JP-A-6-289376. Nos. 8, 278490, 9-81174, and the polymer dispersed liquid crystal type GH mode. That is, one embodiment of the liquid crystal element of the present invention has a polymer medium layer between a pair of electrodes, at least one of which is a transparent electrode, and the polymer medium layer is dispersed in the polymer and the polymer. A polymer dispersed liquid crystal type GH mode liquid crystal element comprising the liquid crystal composition of the present invention.

  Further, the liquid crystal element of the present invention is disclosed in JP-A-6-235931, 6-235940, 6-265859, 7-56174, 9-146124, 9-197388, 10-20346. 10-312207, 10-31216, 10-31231, 10-31232, 10-31233, 10-31234, 10-82986, 10-90674, No. 10-111513, No. 10-111523, No. 10-123509, No. 10-123510, No. 10-206851, No. 10-253993, No. 10-268300, No. 11-149252, JP It can be used for a reflective liquid crystal display described in 2000-2874.

  The liquid crystal element of the present invention may use a liquid crystal composition containing a plurality of dichroic dyes. Further, the liquid crystal composition may have any color. For example, when a black liquid crystal composition is prepared, such as a mixture of a plurality of dichroic dyes, it can be used as a liquid crystal element for monochrome display by applying a voltage. In addition, a liquid crystal element for color display can be produced by preparing liquid crystal compositions colored in red, green and blue, and arranging three kinds of compositions in parallel on a substrate. Further, the liquid crystal element of the present invention may have a laminated structure. For example, three layers of liquid crystal compositions colored yellow, magenta, and cyan are laminated; and blue, green, and red, which are complementary to the liquid crystal compositions colored yellow, magenta, and cyan. A structure in which two layers each having a colored liquid crystal composition arranged in parallel are stacked; and a black colored liquid crystal composition layer and a red, blue and green liquid crystal composition layer The structure which laminates | stacks two layers arrange | positioned side by side; etc. are mentioned.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, substance amounts and ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Example 1: Synthesis example of compound of general formula (I)]
The exemplary compound (1) was synthesized according to the following scheme.

  The synthesis of compound (A) is described in “Liebigs Ann.” (1995); 1319-1326. It carried out by the method of description.

  To a solution of 25.1 g (84.7 mmol) of triphosgene in 20 mL of tetrahydrofuran (THF) was added 45.6 g (203 mmol) of compound (B) (manufactured by Yantai variant Fine Chem.) And 31.0 mL (223 mmol) of triethylamine under ice-cooling. Tetrahydrofuran (THF) 400 mL solution was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was warmed to room temperature and stirred for 6 hours. Hexane and water were added for liquid separation, and the organic layer was washed with saturated brine. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 58.0 g (202 mmol) of compound (C) (99% yield).

To a solution of compound (A) 1.49 g (6.25 mmol) in tetrahydrofuran (THF) 10 mL under ice-cooling, pyridine 1.0 mL (12 mmol) was added, and then compound (C) 2.68 g (9.34 mmol). Of tetrahydrofuran (THF) was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was warmed to room temperature and stirred for 5 hours. Hexane and water were added for liquid separation, and the organic layer was washed with water. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 40/1) to give 2.97 g of Exemplified Compound (1) ( 6.08 mmol) was obtained (yield 97%).
The NMR measurement result and transition temperature measurement result of the product are shown below.
1 H-NMR (CDCl ₃ ): 0.75-1.90 (m, 52H), 2.08 (d, 2H), 4.40-4.62 (m, 2H).
Sm → Ne → Iso.
138 ° C 195 ° C
Sm represents a smectic phase, Ne represents a nematic phase, and Iso represents an isotropic liquid. The number below the arrow is the transition temperature at which the phase transitions from the left phase to the right phase. The same applies hereinafter.

The synthesis | combination of exemplary compound (2) was performed by the method similar to exemplary compound (1).
The NMR measurement result and transition temperature measurement result of the product are shown below.
1 H-NMR (CDCl ₃ ): 0.75-1.90 (m, 56H), 2.08 (d, 2H), 4.40-4.62 (m, 2H).
Sm → N → Iso.
157 ° C 185 ° C

The synthesis | combination of exemplary compound (13) was performed by the method similar to exemplary compound (1).
The NMR measurement result and transition temperature measurement result of the product are shown below.
1 H-NMR (CDCl ₃ ): 0.75-1.90 (m, 56H), 2.10 (d, 2H), 4.40-4.65 (m, 2H).
N → Iso.
48.5 ° C

[Example 2: Phase transition point measurement]
In the following [Table 1-1] and [Table 1-2], the phases of the following exemplary compounds (the compounds of the present invention represented by the general formula (1)), the following compounds for comparative examples, and the compounds for reference examples The transition point and the nematic phase temperature range are shown. The abbreviations in the table indicate SmG: smectic G phase, SmB: smectic B phase, Ne: nematic phase, Iso: isotropic liquid, and the numbers indicate phase transition points (° C.).

From the results shown in [Table 1-1], the exemplary compounds (1) and (2) which are the compounds of the present invention represented by the general formula (I) are comparative compounds which are nematic liquid crystals having no spiro skeleton. Compared with (1) and (2), it can be understood that the nematic liquid crystal compound has a wider temperature range of the nematic phase.
In addition, although it is a compound which has a spiro skeleton, the compound (1) for reference examples outside the range of General formula (1) was a liquid crystal compound which does not become a nematic phase.

＊：例示化合物（１３）は１８℃においてネマチック相を示すが、ネマチック相の下限温度が測定できないため、温度範囲を「３０℃以上」と表記している。

*: Exemplified compound (13) shows a nematic phase at 18 ° C., but since the lower limit temperature of the nematic phase cannot be measured, the temperature range is described as “30 ° C. or higher”.

From the results shown in [Table 1-2], the exemplified compound (13), which is the compound of the present invention represented by the general formula (I), has an Iso point compared to the above exemplified compounds (1) and (2). However, it was found that the temperature range of the nematic phase is sufficiently wide.
In addition, although it is a compound which has a spiro skeleton, the compound (2) for reference examples outside the range of General formula (1) was a liquid crystal compound which does not become a nematic phase.

[Example 3: Solubility in commercial room temperature nematic liquid crystal]
[Table 2] below shows the maximum solubility of the compound represented by the general formula (1) and the comparative compound in a commercially available room-temperature nematic liquid crystal (trade name ZLI-2806, manufactured by E. Merck, Iso point 100 ° C.).

From the results shown in [Table 2], Exemplified Compounds (1) and (2), which are the compounds of the present invention represented by the general formula (I), are nematic liquid crystals “ZLI-2806” (E. Merck) It can be understood that the solubility is higher than those of the compounds for comparative examples (1) and (2) which have good compatibility with the product (manufactured) and have no spiro skeleton.
Moreover, although it is a compound which has a pyro skeleton, even if it compared with the compound (1) for reference examples outside the range of General formula (1), the high solubility was shown.

[Example 4: Preparation of nematic liquid crystal composition]
<Preparation of liquid crystal composition (HLC-1)>
A product name ZLI-2806 (manufactured by E. Merck) (210 mg) and exemplary compound (2) (90 mg) were mixed, and the mixture was heated on a hot plate at 150 ° C. for 1 hour to prepare a liquid crystal composition. The liquid crystal composition was cooled to room temperature and left overnight. The Iso point of the prepared room temperature nematic liquid crystal was 123 ° C.

<Preparation of Liquid Crystal Composition (HLC-2) (Comparative Example)>
A product name ZLI-2806 (manufactured by E. Merck) (240 mg) and comparative compound (2) (60 mg) were mixed, and the mixture was heated on a hot plate at 150 ° C. for 1 hour to prepare a liquid crystal composition. The liquid crystal composition was cooled to room temperature and left overnight. The Iso temperature of the prepared room temperature nematic liquid crystal was 115 ° C.

  From the results shown in [Table 3], when the compound of the present invention represented by the general formula (I) is added, compared with the comparative example without addition, and the comparative example with the addition of the compound not containing the spiro skeleton, In comparison, it was found that a liquid crystal composition having a high maximum temperature of the nematic phase can be prepared.

[Example 5: S value of dichroic dye]
<Synthesis of dichroic dye>
The dichroic dye (D-1) used in the following experiments was synthesized according to the method described in JP-A No. 2003-192664.

<Preparation of liquid crystal composition (LCM-1)>
The liquid crystal composition was prepared by mixing 2.5 mg of the dichroic dye (D-1) and 100 mg of the host liquid crystal (HLC-1) prepared above and heating the mixture on a hot plate at 150 ° C. for 1 hour. Was prepared. The liquid crystal composition was cooled to room temperature and left overnight.

<Preparation of Liquid Crystal Composition (LCM-2) (Comparative Example)>
The liquid crystal composition (LCM-1) was prepared in the same manner as described above except that the host liquid crystal (HLC-1) was changed to the host liquid crystal (HLC-2).

<Preparation of Liquid Crystal Composition (LCM-3) (Comparative Example)>
The liquid crystal composition (LCM-1) was prepared in the same manner as described above except that the host liquid crystal (HLC-1) was changed to ZLI-2806 (manufactured by E. Merck) in <Preparation of liquid crystal composition (LCM-1)>.

<Evaluation of order parameters>
Each of the liquid crystal compositions obtained above was injected into a commercially available liquid crystal cell (KSRP-25, trade name, manufactured by EHC.CO., LTD.) To prepare liquid crystal elements.
The prepared liquid crystal element was irradiated with polarized light parallel to the rubbing direction and polarized light perpendicular to the rubbing direction, and the respective absorption spectra (A‖ and A⊥) were measured with an ultraviolet-visible spectrophotometer (UV2400PC) manufactured by Shimadzu Corporation. It was measured. From A パ ラ メ ー タ and A⊥ at the maximum absorption wavelength, the order parameter (S) was obtained according to the following formula 1. The results are shown in [Table 4].
(Formula 1)
S = (A‖−A⊥) / (A‖ + 2 · A⊥)

  As apparent from the results shown in [Table 4], the liquid crystal composition to which the compound represented by the general formula (I) is added, (LCM-1) does not contain the compound represented by the general formula (I). It was found that higher order parameters were given compared to the liquid crystal compositions (LCM-2, LCM-3).

[Example 6: Measurement of contrast]
<Preparation of liquid crystal composition (CLCM-1)>
Mixing 5 mg of the dichroic dye (D-1) as the dichroic dye, 100 mg of the host liquid crystal (HLC-4), and 0.20 mg of R-1011 (manufactured by E. Merck) as the chiral agent, the mixture Was heated on a hot plate at 130 ° C. for 1 hour to prepare a liquid crystal composition. The liquid crystal composition was cooled to room temperature and left overnight.

<Preparation of liquid crystal composition (CLCM-2)>
It was prepared in the same manner as described above <Preparation of liquid crystal composition (CLCM-1)> except that the host liquid crystal (HLC-1) was changed to ZLI-2806 (manufactured by E. Merck).

<Production of liquid crystal element>
Each of the liquid crystal compositions (CLCM-1 and CLCM-2) obtained above was injected into a liquid crystal cell manufactured by NIPPO ELECTRIC CO., LTD. The substrate for the liquid crystal cell used is a glass substrate (thickness 1.1 mm) on which an ITO transparent electrode layer is formed, has a cell gap of 15 μm, and is provided with an epoxy resin seal. A chemical polyimide alignment film SE-4800 (vertical alignment) is formed.

<Evaluation of contrast ratio>
On the image display surface side of the manufactured liquid crystal element, the contrast ratio (transparency of transparent display / transmittance of color display) was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2400PC). Note that a voltage of 100 Hz and 20 V was applied to the color display side. The results are shown in [Table 5].

  From the results shown in [Table 5], the compound of the present invention (Exemplary Compound (2)), a dichroic dye, a commercially available liquid crystal, and a liquid crystal composition (CLCM-1) containing a chiral agent were used. The liquid crystal element of the present invention can be driven by voltage. In addition, the liquid crystal element has a higher transmittance and a higher display contrast than a liquid crystal element manufactured using the liquid crystal composition (CLCM-2) that does not contain the compound of the present invention. I understood it.

  From the above results, it was confirmed that the compound represented by formula (I) has a wide nematic phase temperature range and high compatibility with the nematic liquid crystal composition. It was also confirmed that the maximum temperature of the nematic phase of the liquid crystal composition can be increased by using a compound represented by the general formula (I) having a high Iso point. Moreover, it was confirmed that the liquid crystal composition containing the compound represented by the general formula (I) improves the S value of the dichroic dye in the liquid crystal. Furthermore, the liquid crystal element manufactured using the liquid crystal composition has a transmittance when no voltage is applied, as compared with a liquid crystal element manufactured using a liquid crystal composition not containing the compound represented by the general formula (I). It was confirmed that the display contrast was increased.

  Since the compound of the present invention exhibits high compatibility with a nematic liquid crystal composition, it is a suitable material for preparing a nematic liquid crystal composition. In particular, when the compound of the present invention is used, a liquid crystal composition having a high maximum temperature of the nematic phase can be prepared. Furthermore, the liquid crystal composition containing the compound of the present invention can be widely used for the production of liquid crystal elements, and gives a high display contrast ratio particularly in guest-host type liquid crystal display elements.

Claims (11)

Compound represented by the following general formula (I):

In the formula, A ¹ and A ² are each independently substituted or unsubstituted 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5. -Represents diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl or pyridazine-3,6-diyl;
Ring B ¹ and Ring B ² constituting the spiro ring are each independently

(* Represents a linking site), Y ¹ and Y ² each independently represent —CH ₂ —, an oxygen atom, or a sulfur atom;
X is the following group

And Z ¹ , Z ² and Z ³ each independently represents an oxygen atom or a sulfur atom;
L ¹ , L ² and L ³ are each independently a single bond, —CH ₂ —, an oxygen atom, a sulfur atom, —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), — CO -, - COO -, - OCO -, - OCOO -, - CO-NR 3 -, - NR 3 -CO -, - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CH 2 _{S -, - SCH 2 -,} - CH = CH -, - C≡C -, - CH 2 -OCO -, - COO-CH 2 -, - OCOO-CH 2 -, - CH 2 -OCOO- or -CH ₂ represents —OCOO—CH ₂ —;
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and one of CH ₂ groups constituting the alkyl group or not adjacent 2 One or more CH ₂ groups may be substituted with oxygen or sulfur atoms;
n and m each represents an integer of 0 to 2. In the general formula (I), spiro ring

The compound according to claim 1, which is any one of the following. The compound according to claim 1 or 2, wherein in the general formula (I), X is -OCOO-. In the said general formula (I), m + n is two or more, The compound of any one of Claims 1-3 characterized by the above-mentioned. It is a liquid crystal compound, The compound of any one of Claims 1-4 characterized by the above-mentioned. A liquid crystal composition comprising at least one of the compounds according to claim 1. The liquid crystal composition according to claim 6, further comprising at least one chiral agent. The liquid crystal composition according to claim 6 or 7, further comprising at least one dichroic dye. A liquid crystal element having a liquid crystal layer between a pair of electrodes, at least one of which is a transparent electrode, wherein the liquid crystal layer contains the liquid crystal composition according to claim 6. 9. A liquid crystal element having a polymer medium layer between a pair of electrodes, at least one of which is a transparent electrode, wherein the polymer medium layer is dispersed in the polymer and the polymer. A liquid crystal device comprising the liquid crystal composition according to item 1. It is a liquid crystal element which has a liquid crystal layer between a pair of electrodes whose at least one is a transparent electrode, Comprising: This liquid crystal layer contains the microcapsule containing the liquid-crystal composition of any one of Claims 6-8. Liquid crystal element.