JP5948832B2 - Optically isotropic liquid crystal composition and optical device containing monofunctional monofunctional monomer - Google Patents

Description

  The present invention relates to a monomer / liquid crystal mixture, a polymer / liquid crystal composite material, and a liquid crystal element containing a monofunctional monofunctional monomer.

Similar to the isotropic phase in the nematic liquid crystal material (hereinafter sometimes referred to as “non-liquid crystal isotropic phase”), the electric birefringence value (isotropic) is also applied to the blue phase, which is a kind of optically isotropic liquid crystal phase. Kerr effect [Δn E ₌ KλE 2 birefringence value) [Delta] n _E is a phenomenon that is proportional to the square of the electric field E induced when an electric field is applied to the sexual medium ^(K: Kerr constant (Kerr constant), lambda: wavelength) ] Is observed.

  In recent years, a mode in which an electric field is applied in an optically isotropic liquid crystal phase such as a blue phase and a polymer-stabilized blue phase to develop electric birefringence has been actively studied (Patent Documents 1 to 11, Non-Patent Documents). Literatures 1-3). In addition to application to display elements in this mode, applications to wavelength tunable filters, wavefront control elements, liquid crystal lenses, aberration correction elements, aperture control elements, optical head devices, etc. using electric birefringence have been proposed. (Patent Documents 6, 10, and 11).

An optically isotropic liquid crystal composition composed of an achiral liquid crystal component and a chiral compound contains a large amount of fluorine compounds, and has a large dielectric anisotropy, a large refractive index anisotropy, a low melting point, and It has a liquid crystal phase over a wide temperature range.
However, although this optically isotropic liquid crystal composition exhibits good electrical characteristics such as a short response time, it has few examples having a liquid crystal phase in a wide temperature range including a low temperature, and should be used as it is as a liquid crystal element. Is difficult.
An optically isotropic polymer / liquid crystal composite material is obtained by polymerizing a monomer / liquid crystal mixture obtained by adding a monomer to an optically isotropic liquid crystal composition at a temperature exhibiting a blue phase or an isotropic phase. . This polymer / liquid crystal composite material has a liquid crystal phase in a wide temperature range including a low temperature, and is extremely useful as a liquid crystal element for a liquid crystal display panel.
As the monomer used for stabilizing the blue phase, a low molecular weight monomer, a macromonomer, an oligomer, or the like can be used. In addition, since the obtained polymer / liquid crystal composite material preferably has a three-dimensional crosslinked structure, it is preferable to use a polyfunctional monomer having two or more polymerizable functional groups. However, this monomer / liquid crystal composition often does not develop a uniform blue phase over a wide temperature range, and the polymer / liquid crystal composite material polymerized with the non-uniform blue phase is non-uniform and uneven in density. As a result, display unevenness occurs in the liquid crystal display panel, which causes a decrease in contrast.
In order for the monomer / liquid crystal mixture to exhibit a uniform blue phase in a relatively wide temperature range, it is effective to use a polyfunctional monomer and a monofunctional monomer in combination. A monomer / liquid crystal mixture in which a polyfunctional monomer and a monofunctional monomer are used in combination exhibits a uniform blue phase in a relatively wide temperature range. Alkyl acrylate, alkyl methacrylate, and the like are known as monofunctional monomers used here. However, this type of monofunctional monomer is not sufficiently compatible with the liquid crystal composition, and a polymer / liquid crystal obtained by polymerizing a monomer / liquid crystal mixture obtained using this type of monofunctional monomer. The composite material is non-uniform and uneven density occurs, or the polymerization temperature margin for obtaining a polymer / liquid crystal composite material with improved density unevenness is narrow. In addition, there is a drawback that a large amount of monomer is necessary for stabilizing the polymer.
In particular, recently, an injection method called “One Drop Filling (ODF) method” has been adopted to inject liquid crystal into a cell. This method is a method in which liquid crystal is dropped on a substrate and the opposite substrate is bonded under vacuum. In this ODF method, liquid crystal droplets are required to be uniform in the plane. When an optically isotropic polymer / liquid crystal composite material is applied to the ODF system, the monomer is polymerized by dropping a mixture of the monomer and the liquid crystal on the substrate and irradiating with ultraviolet light after bonding. Become. At that time, it is often preferable to polymerize near the N * -BP transition temperature of the monomer / liquid crystal mixture, but concentration unevenness is observed in the polymer / liquid crystal composite material obtained by polymerization near this temperature. is there.

JP 2003-327966 A International Publication 2005/90520 JP 2005-336477 A JP 2006-89622 A JP 2006-299084 A International Publication 2005/080529 Special table 2005-537520 Special table 2006-506477 Special table 2007-503487 JP-A-2005-157109 JP 2006-127707 A JP2010-510256

Nature Materials, 1, 64, (2002) Adv. Mater., 17, 96, (2005) Journal of the SID, 14, 551, (2006)

The first object of the invention is to provide a monomer / liquid crystal mixture capable of obtaining a polymer / liquid crystal composite material with improved density unevenness, or a polymerization temperature capable of obtaining a polymer / liquid crystal composite material with improved density unevenness. It is to provide a monomer / liquid crystal mixture with a wide margin.
The second purpose is to have stability against heat, light, etc. by using a polymer / liquid crystal composite material obtained by polymerizing the above monomer / liquid crystal mixture, a short response time, and a large It is an object to provide a liquid crystal element having a polymer-stabilized blue phase that is uniform and has no density unevenness over a wide temperature range including contrast, low driving voltage, and low temperature.

  As a result of diligent research, the present inventors provide a monomer / liquid crystal mixture, a polymer / liquid crystal composite material, and a liquid crystal element using a monofunctional monofunctional monomer, particularly a monofunctional monofunctional monomer having an aromatic ring. As a result, it has been found that the above problems can be significantly improved. Specifically, it is as follows.

  In the present specification, the “liquid crystal compound” is a general term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be abbreviated as a compound, a composition, and an element, respectively.

  In this specification, “liquid crystal element” is a generic term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is a nematic phase-isotropic phase transition temperature, and may simply be abbreviated as clearing point or upper limit temperature. The lower limit temperature of the nematic phase may simply be abbreviated as the lower limit temperature.

  In the present specification, the “monomer / liquid crystal mixture” is a mixture comprising a polymerizable monomer and an optically isotropic liquid crystal composition. The “polymer / liquid crystal composite material” is a composite material composed of a polymer and an optically isotropic liquid crystal composition. “Monofunctional monofunctional monomer” is a polymerizable monomer having one polymerizable functional group and one ring structure. A polymerizable monomer having one polymerizable functional group may be referred to as a “monofunctional monomer”. A “polyfunctional monomer” is a polymerizable monomer having a plurality of polymerizable functional groups, and a polymerizable monomer having two polymerizable functional groups is sometimes referred to as a “bifunctional monomer”.

In the present specification, the compound represented by the formula (1) may be abbreviated as the compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like. In the chemical formula, symbols such as A and B surrounded by hexagons correspond to ring structure A and ring structure B, respectively. These may be abbreviated as “ring A” and “ring B”. “Ring structure” refers to a cyclic group, and includes a phenylene ring, a naphthalene ring, a cyclohexene ring, a bicyclooctane ring, a cyclohexane ring, and the like. Here, a ring structure including a plurality of rings such as a condensed polycyclic hydrocarbon such as a naphthalene ring and a bridged ring hydrocarbon such as a bicyclooctane ring is also counted as one ring structure.
A plurality of the same symbols such as rings A ¹ , Y ¹ , and B are described in the same formula or different formulas, but these may be the same or different.

“Arbitrary” indicates that not only the position but also the number is arbitrary, but the case where the number is 0 is not included. The expression that any A may be replaced by B, C or D is in addition to any A being replaced by B, any A being replaced by C and any A being replaced by D. Thus, it is meant to include the case where a plurality of A are replaced by at least two of B to D. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, and the like. In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced with —O— to become —O—O—. In addition, it is not preferable that the terminal —CH ₂ — in alkyl is replaced by —O—.

  In the present specification, “%” means “% by weight” unless otherwise specified.

式（１）中、
Ｒ^ａは水素、ハロゲン、直鎖状または分岐状の炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい、このアルキル中の任意の水素はハロゲンで置き換えられてもよく；
Ｒ^ｂは単結合、または直鎖状または分岐状の炭素数１〜３０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい、このアルキレン中の任意の水素はハロゲンで置き換えられてもよく；環Ａ^１は１，４−フェニレン、ナフタレン−２，６−ジイル、１，４−シクロヘキセニレン、または１，４−ビシクロ［２，２，２］オクチレンであり、これらの環中の任意の水素は炭素数１〜５のアルキル基、またはハロゲンで置き換えられてもよく、環中の任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、環中の任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく；
Ｘ^１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または単結合であり；
Ｐ^１は、下記の式（Ｍ３−１）〜（Ｍ３−７）のいずれかを表す。

（式中、Ｒ^ｄは、それぞれ独立して水素、ハロゲンまたは炭素数１〜５のアルキルであり、これらのアルキルにおいて任意の水素はハロゲンで置き換えられてもよい。） The present invention includes the following configurations.
[1] A monomer obtained by further mixing at least one polymerizable monomer represented by the general formula (1) with an optically isotropic liquid crystal composition containing an achiral liquid crystal component A and a chiral compound K. / Liquid crystal mixture.

In formula (1),
R ^a is hydrogen, halogen, linear or branched alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH Any hydrogen in the alkyl, which may be replaced with ═CH— or —C≡C—, may be replaced with a halogen;
R ^b is a single bond or a linear or branched alkylene having 1 to 30 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —COO—, —OCO—, —CH Any hydrogen in the alkylene, which may be replaced by ═CH— or —C≡C—, may be replaced by halogen; ring A ¹ is 1,4-phenylene, naphthalene-2,6-diyl, 1,4-cyclohexenylene, or 1,4-bicyclo [2,2,2] octylene, and any hydrogen in these rings may be substituted with an alkyl group having 1 to 5 carbon atoms or halogen. Well, any —CH ₂ — in the ring may be replaced with —O—, and any —CH═ in the ring may be replaced with —N═;
X ¹ is —O—, —CO—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ — or a single bond;
P ¹ represents any of the following formulas (M3-1) to (M3-7).

(In the formula, each R ^d is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen may be replaced by halogen.)

式（２）中、
Ｒ^ａは、直鎖状または分岐状の炭素数１〜３０のアルキル、炭素数２〜３０のアルケニル、または炭素数１〜３０のアルコキシであり、このアルキル中の任意の水素はハロゲンで置き換えられてもよく；
Ｒ^ｂは単結合、直鎖状または分岐状の炭素数１〜３０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい、このアルキレン中の任意の水素はハロゲンで置き換えられてもよく；
Ｘ^１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または単結合であり；
Ｑ^１、Ｑ^２、Ｑ^３、およびＱ^４はそれぞれ独立に水素、フッ素、塩素、またはメチル基であり；
Ｒ^ｄは水素またはメチルであり、Ｐ^１は式（Ｍ３−３）または（Ｍ３−７）を表す。 [2] The monomer / liquid crystal mixture according to claim 1, wherein the polymerizable monomer is represented by the general formula (2).

In formula (2),
R ^a is linear or branched alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or alkoxy having 1 to 30 carbon atoms, and any hydrogen in the alkyl is replaced by halogen. May be;
R ^b is a single bond, linear or branched alkylene having 1 to 30 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CH═CH— or —C≡C—. Any hydrogen in the alkylene may be replaced with a halogen;
X ¹ is —O—, —CO—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ — or a single bond;
Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently a hydrogen, fluorine, chlorine, or methyl group;
R ^d is hydrogen or methyl, and P ¹ represents the formula (M3-3) or (M3-7).

式（２−１）〜（２−３）中、
Ｒ^ａは、直鎖状または分岐状の炭素数１〜３０のアルキル、または直鎖状または分岐状の炭素数２〜３０のアルケニルであり；
Ｒ^ｂは直鎖状または分岐状の炭素数１〜３０のアルキレンであり；
Ｑ^１、Ｑ^２、Ｑ^３、およびＱ^４はそれぞれ独立に水素、フッ素、またはメチル基であり；
Ｒ^ｄは水素またはメチルである。 [3] The monomer / liquid crystal mixture according to [2], wherein the polymerizable monomer is represented by any one of the general formulas (2-1) to (2-3).

In formulas (2-1) to (2-3),
R ^a is linear or branched alkyl having 1 to 30 carbon atoms, or linear or branched alkyl having 2 to 30 carbon atoms;
R ^b is a linear or branched alkylene having 1 to 30 carbon atoms;
Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently hydrogen, fluorine, or a methyl group;
R ^d is hydrogen or methyl.

[4] In Formula (2-1), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains a polymerizable monomer that is hydrogen.

[5] In Formula (2-1), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains a polymerizable monomer that is methyl.

[6] In Formula (2-2), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains a polymerizable monomer that is hydrogen.

[7] In Formula (2-2), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains at least one polymerizable monomer that is methyl.

[8] In Formula (2-3), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains a polymerizable monomer that is hydrogen.

[9] In Formula (2-3), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is The monomer / liquid crystal mixture according to [3], which contains a polymerizable monomer that is methyl.

（一般式（１−Ａ）において、Ｒ^１１は水素、炭素数１〜２０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−または−Ｃ≡Ｃ−で置き換えられてもよいが、２つの連続する−ＣＨ_２−が−Ｏ−で置き換えられることはなく、このアルキル中の任意の水素はハロゲンで置き換えられてもよく； 環Ａ^１１、環Ａ^１２、環Ａ^１３および環Ａ^１４は独立して、１，４−フェニレン、１，３−ジオキサン−２、５―ジイル、テトラヒドロピラン−２，５−ジイル、テトラヒドロピラン−３，６−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−２，６−ジイル、ビシクロ［２，２，２］オクタン−１，４−ジイル、１，４−シクロヘキシレン、または２，６，７−トリオキサビシクロ［２，２，２］オクタン−１，４−ジイルであり、これらの環中の任意の水素はハロゲンで置き換えられてもよく； Ｚ^１１、Ｚ^１２、Ｚ^１３およびＺ^１４は独立して、単結合、炭素数１〜４のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＳＯ−、−ＯＣＳ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、このアルキレン中の任意の水素はハロゲンで置き換えられてもよく；Ｌ^１１およびＬ^１２はそれぞれ独立して水素またはハロゲンであり；Ｘ^１１はハロゲン、−Ｃ≡Ｎ、−Ｎ＝Ｃ＝Ｓ、−Ｃ≡Ｃ−Ｃ≡Ｎ、−ＳＦ_５、−ＣＨＦ_２、−ＣＦ_３、−ＣＦ_２ＣＨ_２Ｆ、−ＣＦ_２ＣＨＦ_２、−ＣＦ_２ＣＦ_３、−（ＣＦ_２）_３−Ｆ、−ＣＦ_２ＣＨＦＣＦ_３、−ＣＨＦＣＦ_２ＣＦ_３、−（ＣＦ_２）_４−Ｆ、−（ＣＦ_２）_５−Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＯＣＦ_２ＣＨ_２Ｆ、−ＯＣＦ_２ＣＨＦ_２、−ＯＣＨ_２ＣＦ_３、−ＯＣＦ_２ＣＦ_３、−Ｏ−（ＣＦ_２）_３−Ｆ、−ＯＣＦ_２ＣＨＦＣＦ_３、−ＯＣＨＦＣＦ_２ＣＦ_３、−Ｏ−（ＣＦ_２）_４−Ｆ、−Ｏ−（ＣＦ_２）_５−Ｆ、−ＣＨ＝ＣＦ_２、−ＣＨ＝ＣＨＣＦ_３、または−ＣＨ＝ＣＨＣＦ_２ＣＦ_３； ｌおよびｍは独立して、０または１である。） [10] The monomer / liquid crystal mixture according to any one of [1] to [9], wherein the achiral liquid crystal component A contains a compound represented by the general formula (1-A).

(In the general formula (1-A), R ¹¹ is hydrogen, alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, — OCO- or —C≡C— may be replaced, but two consecutive —CH ₂ — are not replaced by —O—, and any hydrogen in the alkyl may be replaced by halogen. Ring A ¹¹ , ring A ¹² , ring A ¹³ and ring A ¹⁴ are independently 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran; -3,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2,2,2] octane-1,4-diyl, 1,4 -Cyclohexylene, or 2, , 7-Trio key is rust cyclo [2,2,2] octane-1,4-diyl, any hydrogen in these rings may be replaced by halogen; ^{Z 11,} Z ^{12, Z 13} and Z ¹⁴ is independently a single bond or alkylene having 1 to 4 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —S—, —COO—, —OCO—, —CSO—. , -OCS-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen in the alkylene may be replaced by halogen; L ¹¹ and L ¹² Are each independently hydrogen or halogen; X ¹¹ is halogen, —C≡N, —N═C═S, —C≡C—C≡N, —SF ₅ , —CHF ₂ , —CF ₃ , — _{CF 2 CH 2 F, -CF 2} CHF 2, -CF 2 _{F 3, - (CF 2)} 3 -F, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CF 2) 4 -F, - (CF 2) 5 -F, -OCHF 2, -OCF 3, _{-OCF 2 CH 2 F, -OCF 2} CHF 2, -OCH 2 CF 3, -OCF 2 CF 3, -O- (CF 2) 3 -F, -OCF 2 CHFCF 3, -OCHFCF 2 CF 3, -O _{- (CF 2) 4 -F,} -O- (CF 2) 5 -F, -CH = CF 2, -CH = CHCF 3 or _{-CH = CHCF 2 CF 3,;} l and m are independently 0 Or 1.

（式（１−Ａａ）〜（１−Ａｊ）中、Ｒ^１１は炭素数２〜８のアルキルであり、Ｘ^１１はフッ素、塩素、−Ｃ≡Ｎ、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＯＣＨ_２Ｆまたは−Ｃ＝Ｃ−ＣＦ_３であり、（Ｆ）は水素またはフッ素を示す。） [11] The achiral liquid crystal component A contains one or more compounds represented by any of the following formulas (1-Aa) to (1-Aj) [1] to [9] The monomer / liquid crystal mixture according to any one of the above.

(In the formulas (1-Aa) to (1-Aj), R ¹¹ is alkyl having 2 to 8 carbon atoms, and X ¹¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH. ₂ F, —OCF ₃ , —OCHF ₂ , —OCH ₂ F or —C═C—CF ₃ , (F) represents hydrogen or fluorine.)

（式（Ｋ１）〜（Ｋ５）中、Ｒ^Ｋは独立して、水素、ハロゲン、−Ｃ≡Ｎ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝Ｓまたは炭素数１〜２０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよい、このアルキル中の任意の水素はハロゲンで置き換えられてもよく； Ａ^Ｋは独立して、芳香族性の６〜８員環、非芳香族性の３〜８員環、
または、炭素数９〜２０の縮合環であり、これらの環中の任意の水素はハロゲン、炭素数１〜３のアルキルまたはハロアルキルで置き換えられてもよく、環の−ＣＨ_２−は−Ｏ−、−Ｓ−または−ＮＨ−で置き換えられてもよく、−ＣＨ＝は−Ｎ＝で置き換えられてもよく；
Ｙ^Ｋは独立して、水素、ハロゲン、炭素数１〜３のアルキル、炭素数１〜３のハロアルキル、芳香族性の６〜８員環、非芳香族性の３〜８員環、または、炭素数９〜２０の縮合環であり、これらの環の任意の水素がハロゲン、炭素数１〜３のアルキルまたはハロアルキルで置き換えられてもよく、−ＣＨ_２−は−Ｏ−、−Ｓ−または−ＮＨ−で置き換えられてもよく、−ＣＨ＝は−Ｎ＝で置き換えられてもよく；Ｚ^Ｋは独立して単結合、または炭素数１〜８のアルキレンであるが、任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＳＯ−、−ＯＣＳ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく；Ｘ^Ｋは単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＨ_２ＣＨ_２−であり；ｍＫは１〜４の整数である。） [12] The liquid crystal component A contains one or more compounds represented by the general formula (1-A), and the chiral component K includes compounds represented by the general formulas (K1) to (K5). The monomer / liquid crystal mixture according to any one of [1] to [9], which contains one or more kinds.

(In the formula (K1) ~ (K5), R K is independently hydrogen, halogen, -C≡N, alkyl having -N = C = O, -N = C = S or C 1-20 And any —CH ₂ — in the alkyl is replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—. Any hydrogen in the alkyl may be replaced by a halogen; ^AK is independently an aromatic 6-8 membered ring, a non-aromatic 3-8 membered ring,
Alternatively, it is a condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced with halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — in the ring is —O—. , -S- or -NH-, and -CH = may be replaced by -N =;
Y ^K is independently hydrogen, halogen, alkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, aromatic 6 to 8 membered ring, non-aromatic 3 to 8 membered ring, or A condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — may be —O—, —S— or It may be replaced by -NH-, -CH = may be replaced by -N =; ^{Z K} is independently a single bond, or an alkylene having 1 to 8 carbon atoms, arbitrary -CH ₂ -Is -O-, -S-, -COO-, -OCO-, -CSO-, -OCS-, -N = N-, -CH = N-, -N = CH-, -CH = CH-. , -CF = CF- or -C≡C-, where any hydrogen is replaced by halogen Well; ^{X K} is a single _{bond, -COO -, - OCO -,} - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, or _-CH 2 CH ₂ - and are; mK is It is an integer of 1-4. )

[13] In the achiral liquid crystal component A, the content of the compound represented by the general formula (1-A) is 50 to 100% by weight, and in the chiral component K, the general formulas (K1) to ( The monomer / liquid crystal mixture according to any one of [1] to [9], wherein one or more of the compounds represented by K5) is 0.1 to 30% by weight.

ここで、基（Ｍ３−１）〜基（Ｍ３−７）におけるＲ^ｄは、それぞれ独立して水素、ハロゲンまたは炭素数１〜５のアルキルであり、これらのアルキルにおいて任意の水素はハロゲンで置き換えられてもよい。 [14] The monomer / liquid crystal mixture according to any one of [1] to [12], further containing one or more types of bifunctional monomers represented by the general formula (M2).

^{R C -Y M - (A M} -Z M) m1 -A M -Y M -R C (M2)

In formula (M2), R ^C each independently represents a polymerizable group of groups (M3-1) to (M3-7); A ^M is each independently aromatic or non-aromatic. A 5-membered ring, a 6-membered ring or a condensed ring having 9 to 20 carbon atoms, in which —CH ₂ — is —O—, —NH—, or —NCH ₃ —, and —CH ₂ — = May be replaced by -N =, and the hydrogen atom in the ring may be replaced by halogen and alkyl having 1 to 5 carbon atoms or alkyl halide; Y ^M is independently a single bond or carbon An alkylene having a number of 1 to 20, in which any —CH ₂ — is replaced by —O—, —S—, —CH═CH—, —C≡C—, —COO—, or —OCO—; It is well also; ^{Z M} are each independently a single _{bond, - (CH 2) m3 -} , - _{(CH 2) m3 -, -} (CH 2) m3 O -, - O (CH 2) m3 O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - (CF 2 ) ₂ −, — (CH ₂ ) ₂ —COO—, —OCO— (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH—, —C≡C—COO—, —OCO —C≡C—, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH —C≡C—, —OCF ₂ — (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CF ₂ O—, —OCF ₂ — or —CF ₂ O— (wherein m3 is 1 to 20 M1 is an integer from 1 to 6;

Here, R ^d in the group (M3-1) to the group (M3-7) is each independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen is replaced with halogen. May be.

式中、Ｒ^Ｃは１〜３０のアクリレート基、もしくはメタクリレート基であり； Ｙ^Ｍはそれぞれ独立して単結合、または炭素数１〜２０のアルキレンであり； Ｚ^Ｍはそれぞれ独立して単結合、−（ＣＨ₂）_ｍ３−、−Ｏ（ＣＨ₂）_ｍ３−、−（ＣＨ₂）_ｍ３Ｏ−、−Ｏ（ＣＨ₂）_ｍ３Ｏ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−（ＣＦ₂）₂−、−（ＣＨ₂）_２−ＣＯＯ−、−ＯＣＯ−（ＣＨ₂）_２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−（ＣＨ₂）₂−、−（ＣＨ₂）₂−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−Ｃ≡Ｃ−、−ＯＣＦ_２−（ＣＨ₂）_２−、−（ＣＨ₂）_２−ＣＦ_２Ｏ−、−ＯＣＦ_２−または−ＣＦ_２Ｏ−（前記式中、ｍ^３は１〜２０の整数である）であり； また１，４−フェニレンと（Ｆ）を直線で結んだ表記は、１つまたは２つの水素がフッ素で置き換えられていてもよい１，４−フェニレンを表し、また１，４−フェニレンと（Ｆ，Ｍｅ）を直線で結んだ表記は、１つまたは２つの水素がフッ素またはメチルで置き換えられていてもよい１，４−フェニレンを表す。 [15] The monomer / liquid crystal mixture according to any one of [1] to [12], further containing one or more types of bifunctional monomers represented by the general formula (M2-15).

In the formula, R ^C is an acrylate group having 1 to 30 or a methacrylate group; Y ^M is each independently a single bond or alkylene having 1 to 20 carbon atoms; Z ^M is each independently a single bond; _{- (CH 2) m3 -,} - O (CH 2) m3 -, - (CH 2) m3 O -, - O (CH 2) m3 O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - ( CF 2) 2 -, - (CH 2) 2 -COO -, - OCO- (CH 2) 2 -, - CH = CH-COO -, - OCO-CH = CH-, -C≡C-COO -, - OCO- C≡C -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - CF = CF -, - C≡C -CH = CH -, - CH = CH-C≡C -, - OCF 2 - (CH 2) 2 -, - (CH 2) 2 -CF 2 O -, - OCF ₂ — or —CF ₂ O— (wherein m ³ is an integer of 1 to 20); and 1,4-phenylene and (F) are connected by a straight line, one or two One hydrogen represents 1,4-phenylene which may be replaced by fluorine, and 1,4-phenylene and (F, Me) are connected by a straight line when one or two hydrogens are fluorine or methyl. It represents 1,4-phenylene which may be replaced.

[16] The monomer according to any one of [1] to [15], which exhibits a chiral nematic phase at a temperature of −20 ° C. to 70 ° C. and has a helical pitch of 700 nm or less in at least a part of this temperature range. / Liquid crystal mixture.

[17] A polymer / liquid crystal composite material used in an element driven in an optically isotropic liquid crystal phase, obtained by polymerizing the monomer / liquid crystal mixture according to [1] to [16].

[18] An optically isotropic liquid crystal phase obtained by polymerizing the monomer / liquid crystal mixture according to [1] to [16] with an non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase. Polymer / liquid crystal composite material used for driven elements.

[19] An electrode is disposed on one or both surfaces, and an electric field is applied to the liquid crystal composition or polymer / liquid crystal composite material disposed between the substrates, and the liquid crystal composition or polymer / liquid crystal composite material via the electrode. A liquid crystal device comprising an electric field applying means for performing the above operation, wherein the polymer / liquid crystal composite material is [17] or [18].

The optically isotropic monomer / liquid crystal composition of the present invention exhibits a blue phase in a relatively wide temperature range and exhibits good compatibility.
The polymer / liquid crystal composite material obtained by polymerizing this optically isotropic monomer / liquid crystal composition in the blue phase or the isotropic phase is optically isotropic with no concentration unevenness over a wide temperature range. A liquid crystal phase (including a blue phase), a relatively low driving voltage, and a high response speed. The optically isotropic liquid crystal composition and polymer / liquid crystal composite material according to a preferred embodiment of the present invention can be used in a wide temperature range.
The monomer / liquid crystal mixture and polymer / liquid crystal composite material according to preferred embodiments of the present invention can be suitably used for liquid crystal elements such as display elements based on these effects.

The comb-shaped electrode substrate used in the Example is shown. The optical system used in the Example is shown.

1 Optically Isotropic Liquid Crystal Composition The optically isotropic liquid crystal composition used in the present invention contains an achiral liquid crystal component and a chiral compound. Here, the chirality of the chiral compound does not matter.
The compound contained in the liquid crystal composition used in the present invention is generally synthesized by a known method, for example, a method of reacting necessary components at a high temperature.
Further, each element of the compound constituting the liquid crystal composition used in the present invention can be an analogue composed of an isotope element as long as there is no significant difference in physical properties.

1.1 Optically Isotropic Liquid Crystal Phase The liquid crystal composition used in the present invention has an optically isotropic liquid crystal phase. Here, the liquid crystal composition has optical isotropy. Macroscopically, the liquid crystal molecular alignment is isotropic, so it is optically isotropic, but microscopically there is liquid crystal order. To do.
In the present specification, the “optically isotropic liquid crystal phase” means a phase that expresses an optically isotropic liquid crystal phase rather than a fluctuation, for example, a phase that expresses a platelet structure (blue in a narrow sense). Phase) is an example.

  In general, blue phases are classified into three types (blue phase I, blue phase II, blue phase III), and these three types of blue phases are all optically active and isotropic. In the blue phase I or blue phase II, two or more types of diffracted light caused by Bragg reflection from different lattice planes are observed.

  In the optically isotropic liquid crystal composition used in the present invention, in order to develop an optically isotropic liquid crystal phase, a helical pitch based on microscopic liquid crystal order (hereinafter simply referred to as “pitch”). Is preferably 1000 nm or less.

  The electrical birefringence in the optically isotropic liquid crystal phase increases as the pitch increases, so as long as the desired optical properties (transmittance, diffraction wavelength, etc.) are satisfied, the type and content of the chiral compound are adjusted, Electric birefringence can be increased by setting the pitch long.

  In the present specification, “non-liquid crystal isotropic phase” is a generally defined isotropic phase, that is, a disordered phase, and even if a region where the local order parameter is not zero is generated, the cause Is isotropic phase due to fluctuations. For example, an isotropic phase appearing on the high temperature side of the nematic phase corresponds to a non-liquid crystal isotropic phase in this specification. The same definition shall apply to the chiral liquid crystal in this specification.

  The temperature range of the optically isotropic liquid crystal composition is such that a chiral compound is added to a liquid crystal composition having a wide coexistence temperature range of a nematic phase or a chiral nematic phase and an isotropic phase, and the optically isotropic liquid crystal composition is It can be widened by developing a liquid crystal phase. For example, a liquid crystal compound having a high clearing point and a liquid crystal compound having a low clearing point are mixed to prepare a liquid crystal composition having a wide coexisting temperature range of a nematic phase and an isotropic phase over a wide temperature range, and a chiral compound is added thereto. Thus, a composition that exhibits an optically isotropic liquid crystal phase in a wide temperature range can be prepared.

  As the liquid crystal composition having a wide coexistence temperature range of the nematic phase or the chiral nematic phase and the isotropic phase, the difference between the upper limit temperature and the lower limit temperature at which the chiral nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C. A liquid crystal composition is preferable, and a liquid crystal composition having a difference of 5 to 150 ° C. is more preferable. Further, a liquid crystal composition having a difference between the upper limit temperature and the lower limit temperature at which the nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C.

When an electric field is applied to the liquid crystal medium used in the present invention in an optically isotropic liquid crystal phase, electric birefringence occurs, but the Kerr effect is not necessarily required.
Since the electrical birefringence in the optically isotropic liquid crystal phase increases as the pitch increases, the type and content of the chiral agent can be adjusted as long as the requirements of other optical properties (transmittance, diffraction wavelength, etc.) are satisfied. Thus, the electric birefringence can be increased by setting the pitch long.

1.2 Liquid crystal component A
The optically isotropic liquid crystal composition used in the present invention contains an achiral liquid crystal component A containing at least one compound represented by the formula (1-A) as an essential component.

上記式（１−Ａ）において、Ｒ^１１は水素、炭素数１〜２０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−または−Ｃ≡Ｃ−で置き換えられてもよいが、２つの連続する−ＣＨ_２−が−Ｏ−で置き換えられることはなく、このアルキル中の任意の水素はハロゲンで置き換えられてもよい。

In the above formula (1-A), R ¹¹ is hydrogen, alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, —OCO. - or it may be replaced by -C≡C-, but two consecutive -CH 2 _- never is replaced by -O-, and any hydrogen in the alkyl can be replaced by halogen.

In such R ¹¹ , alkenyl having 1 to 10 carbon atoms and 2 to 10 carbon atoms is preferable. More preferred are alkyl and alkenyl having 2 to 8 carbon atoms. The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3, and _{-C 2 H} 4 CH = CHC 2 In alkenyl having a double bond at odd positions such as H ₅ , the trans configuration is preferable. -CH ₂ CH ₌ CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as _{-CH 2 CH = CHC 2 H 5} , and _-CH 2 CH = _CHC 3 _{H 7} are preferred. An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.

In the above formula (1-A), ring A ¹¹ , ring A ¹² , ring A ¹³ and ring A ¹⁴ are independently 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran- 2,5-diyl, tetrahydropyran-3,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2,2,2] octane-1 , 4-diyl, 1,4-cyclohexylene, or 2,6,7-trioxabicyclo [2,2,2] octane-1,4-diyl, and any hydrogen in these rings is halogen. It may be replaced.

Ring A ¹¹ , Ring A ¹² , Ring A ¹³ and Ring A ¹⁴ are each independently 1,4-phenylene, 1,3-dioxane-2,5-diyl, or 2, It is preferably 6,7-trioxabicyclo [2,2,2] octane-1,4-diyl.

In the above formula (1-A), Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently a single bond or alkylene having 1 to 4 carbon atoms, and any —CH ₂ — in the alkylene is -O-, -S-, -COO-, -OCO-, -CSO-, -OCS-, -CH = CH-, -CF = CF- or -C≡C- Any hydrogen therein may be replaced by halogen.

^{Z 11,} Z 12, Z ¹³ and ^{Z 14} is a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - COO -, - CF 2 O -, - CH 2 O- or -OCH ₂ -. among them, a single bond, -COO- or _-CF 2 O-are preferred.
In these bonds, double bonds such as —CH═CH—, —CF═CF—, —CH═CH— (CH ₂ ) ₂ —, and — (CH ₂ ) ₂ —CH═CH— In the linking group having a steric configuration, trans is preferable to cis.

In the above formula (1-A), L ¹¹ and L ¹² are each independently hydrogen or halogen. Among these, L ¹¹ and L ¹² are preferably each independently hydrogen or fluorine.

In the above formula (1-A), X ¹¹ is halogen, —C≡N, —N═C═S, —C≡C—C≡N, —SF ₅ , —CHF ₂ , —CF ₃ , —CF _{2. CH 2 F, -CF 2 CHF 2} , -CF 2 CF 3, - (CF 2) 3 -F, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CF 2) 4 -F, - (CF 2 ) ₅ -F, -OCHF ₂ , -OCF ₃ , -OCF ₂ CH ₂ F, -OCF ₂ CHF ₂ , -OCH ₂ CF ₃ , -OCF ₂ CF ₃ , -O- (CF ₂ ) ₃ -F,- _{OCF 2 CHFCF 3, -OCHFCF 2 CF} 3, -O- (CF 2) 4 -F, -O- (CF 2) 5 -F, -CH = CF 2, -CH = CHCF 3 or -CH = CHCF, it is a ₂ CF _3.

Preferred examples of X ¹¹ are fluorine, chlorine, —C≡N, —N═C═S, —CF ₃ , —CHF ₂ , —OCF ₃ and —OCHF ₂ . More preferred examples of X ¹¹ are fluorine, chlorine, —C≡N, —N═C═S, —CF ₃ and —OCF ₃ .

  In the formula (1-A), l and m are independently 0 or 1.

（式（１−Ａａ）〜（１−Ａｊ）中、Ｒ^１１は炭素数２〜８のアルキルであり、Ｘ^１１はフッ素、塩素、−Ｃ≡Ｎ、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＯＣＨ_２Ｆまたは−Ｃ＝Ｃ−ＣＦ_３であり、（Ｆ）は水素またはフッ素を示す。）
化合物（１−Ａ）におけるｌおよびｍの組み合わせ、環Ａ^１１〜Ａ^１４の種類、末端基Ｒ^２、末端のフェニレン環上の基およびその置換位置（Ｌ^１、Ｌ^２およびＸ^１）、結合基Ｚ^１１〜Ｚ^１４等を適切に選択することによって、液晶成分Ａの透明点、屈折率異方性、誘電率異方性等の物性を調整することが可能である。
ｌおよびｍの組み合わせ、環Ａ^１１〜Ａ^１４、末端基Ｒ^１１、末端基Ｘ^１１、結合基Ｚ^１１〜Ｚ^１４、Ｌ^１１およびＬ^１２の種類等と、化合物（１−Ａ）の物性との一般的な関係を以下に説明する。 As the compound represented by the above formula (1-A), compounds represented by the following formulas (1-Aa) to (1-Aj) are particularly preferable.

(In the formulas (1-Aa) to (1-Aj), R ¹¹ is alkyl having 2 to 8 carbon atoms, and X ¹¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH. ₂ F, —OCF ₃ , —OCHF ₂ , —OCH ₂ F or —C═C—CF ₃ , (F) represents hydrogen or fluorine.)
Combination of l and m in compound (1-A), types of rings A ^{11 to} A ¹⁴ , terminal group R ² , groups on the terminal phenylene ring and their substitution positions (L ¹ , L ² and X ¹ ), bond By appropriately selecting the groups Z ^{11 to} Z ^{14 and the} like, it is possible to adjust physical properties such as the clearing point, refractive index anisotropy, dielectric constant anisotropy, etc. of the liquid crystal component A.
a combination of 1 and m, ring A ^{11 to} A ¹⁴ , terminal group R ¹¹ , terminal group X ¹¹ , bonding group Z ^{11 to} Z ¹⁴ , types of L ¹¹ and L ¹² , etc., and physical properties of compound (1-A) The general relationship of will be described below.

  In general, the larger the l + m, the higher the clearing point of the compound (1-A), and the smaller the l + m, the lower the melting point of the compound (1-A).

Generally, the more the aromatic rings are contained in the rings A ^{11 to} A ¹⁴ , the greater the refractive index anisotropy of the compound (1-A). 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5- in which any hydrogen is replaced by halogen Diyl, or 2,6,7-trioxabicyclo [2,2,2] octane-1,4-diyl is effective in developing a large dielectric anisotropy, and 1,4-cyclohexylene, and tetrahydropyran- 2,5-diyl contributes to good compatibility expression of the compound (1-A).

In general, when each of R ¹¹ is linear, the temperature range of the liquid crystal phase of the compound (1-A) is wide and the viscosity is small. On the other hand, when R ¹¹ is a branched chain, the compatibility of the compound (1-A) with other liquid crystal compounds is improved.

In general, the linking groups Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each a single bond, —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O. _{-, - OCH 2 -, -} CF = CF -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - (CH 2) 2 -CF 2 O -, - OCF 2 - ( When it is CH ₂ ) ₂ — or — (CH ₂ ) ₄ —, the viscosity of the compound (1-A) is small. In general, the linking groups Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ — or —CH═CH—. In this case, the viscosity of the compound (1-A) is further reduced. In general, when the bonding groups Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each —C≡C—, the compound (1-A) has a large refractive index anisotropy. In general, when the bonding groups Z ¹¹ , Z ¹² , Z ^13, and Z ¹⁴ are —COO— or —CF ₂ O—, the compound (1-A) has a large dielectric anisotropy. In general, the linking groups Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are single bonds, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ — or — (CH ₂ ) 4 _- when a compound (1-a) is relatively, a chemically stable, deterioration hardly occurs.
In general, when the refractive index anisotropy or the dielectric anisotropy is large, the liquid crystal element of the present invention tends to have a low voltage, and when the viscosity is low, the response speed increases.

In general, X ¹¹ is fluorine, chlorine, —C≡N, —N═C═S, —SF ₅ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or —OCH. _{When 2} F, the dielectric anisotropy of the compound (1-A) is large. In general, when X ¹¹ is —C≡N or —N═C═S, the optical anisotropy of the compound (1-A) is large. When X ¹¹ is fluorine, —OCF ₃ or alkyl, it is chemically stable.

Generally, L ¹¹ and L ¹² are both fluorine, X ¹¹ is fluorine, chlorine, —C≡N, —N═C═S, —SF ₅ , —CF ₃ , —CHF ₂ , —CH ₂ F , —OCF ₃ , —OCHF ₂ or —OCH ₂ F, the compound (1-A) has a large dielectric anisotropy. In general, when L ¹¹ is fluorine and X ¹¹ is —CF ₃ or —OCF ₃ , when L ¹¹ and L ¹² are both fluorine and X ¹¹ is —CF ₃ or —OCF ₃ , Alternatively, when L ¹¹ , L ¹² and X ¹¹ are all fluorine, the compound (1-A) has a large dielectric anisotropy value, a wide temperature range of the liquid crystal phase, and is chemically stable and deteriorated. Hard to wake up.

式（Ｋ１）〜（Ｋ５）中、Ｒ^Ｋは独立して、水素、ハロゲン、−Ｃ≡Ｎ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝Ｓまたは炭素数１〜２０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよいが、２つの連続する−ＣＨ_２−が−Ｏ−で置き換えられることはなく、このアルキル中の任意の水素はハロゲンで置き換えられてもよく；Ａ^Ｋは独立して、芳香族性あるいは非芳香族性の３〜８員環、または、炭素数９〜２０の縮合環であり、これらの環中の任意の水素はハロゲン、炭素数１〜３のアルキルまたはハロアルキルで置き換えられてもよく、−ＣＨ_２−は−Ｏ−、−Ｓ−または−ＮＨ−で置き換えられてもよく、−ＣＨ＝は−Ｎ＝で置き換えられてもよく；Ｙ^Ｋは独立して、水素、ハロゲン、炭素数１〜３のアルキル、炭素数１〜３のハロアルキル、芳香族性または非芳香族性の３から８員環、または、炭素数９〜２０の縮合環であり、これらの環中の任意の水素はハロゲン、炭素数１〜３のアルキルまたはハロアルキルで置き換えられてもよく、−ＣＨ_２−は−Ｏ−、−Ｓ−または−ＮＨ−で置き換えられてもよく、−ＣＨ＝は−Ｎ＝で置き換えられてもよく； Ｚ^Ｋは独立して単結合、または炭素数１〜８のアルキレンであるが、任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＳＯ−、−ＯＣＳ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく； Ｘ^Ｋは単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＨ_２ＣＨ_２−であり； ｍＫは１〜４である。
これらの中でも、液晶組成物に添加されるキラル化合物としては、式（Ｋ２）に含まれる式（Ｋ２−１）〜式（Ｋ２−８）、式（Ｋ４）に含まれる式（Ｋ４−１）〜式（Ｋ４−６）および、式（Ｋ５）に含まれる式（Ｋ５−１）〜式（Ｋ５−３）が好ましい。 1.3 Chiral Compound As the chiral compound contained in the optically isotropic liquid crystal composition, a compound having a large twisting power is preferable. A compound having a large torsional force can reduce the amount of addition necessary for obtaining a desired pitch, and therefore, an increase in driving voltage can be suppressed, which is practically advantageous. Specifically, compounds represented by the following formulas (K1) to (K5) are preferable.

In formulas (K1) to (K5), R ^K is independently hydrogen, halogen, —C≡N, —N═C═O, —N═C═S, or alkyl having 1 to 20 carbons, Any —CH ₂ — in the alkyl may be replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—. Although two consecutive —CH ₂ — may not be replaced by —O—, any hydrogen in the alkyl may be replaced by halogen; ^AK is independently aromatic or non- An aromatic 3- to 8-membered ring or a condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, -CH ₂ - is -O -, - it may be replaced by S- or -NH-, -C = May be replaced by -N =; Y ^K is independently hydrogen, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, from 3 aromatic or nonaromatic An 8-membered ring or a condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — is — O—, —S— or —NH— may be substituted, —CH═ may be substituted with —N═; Z ^K is independently a single bond or alkylene having 1 to 8 carbon atoms. Any —CH ₂ — is —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —N═N—, —CH═N—, —N═CH -, -CH = CH-, -CF = CF- or -C≡C- Hydrogen may be replaced by halogen; ^{X K} is a single _{bond, -COO -, - OCO -,} - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, or -CH ₂ CH ₂ —; mK is 1-4.
Among these, as the chiral compound added to the liquid crystal composition, the formula (K2-1) to the formula (K2-8) included in the formula (K2) to the formula (K4-1) included in the formula (K4). To Formula (K4-6) and Formula (K5-1) to Formula (K5-3) included in Formula (K5) are preferable.

（式中、Ｒ^Ｋは独立して、炭素数３〜１０のアルキルであり、このアルキル中の環に隣接する−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよい。）。
一般的に、本発明に使用される光学的等方性の液晶組成物におけるキラル化合物の含有量は、１〜２０重量％が好ましく、１〜１０重量％が特に好ましい。これらの範囲でキラル化合物を含有する液晶組成物は、光学的に等方性の液晶相を有するようになりやすくなる。

(Wherein, R ^K is independently alkyl having 3 to 10 carbon atoms, and —CH ₂ — adjacent to the ring in this alkyl may be replaced by —O—, and any —CH ₂ — May be replaced by -CH = CH-).
Generally, the content of the chiral compound in the optically isotropic liquid crystal composition used in the present invention is preferably 1 to 20% by weight, particularly preferably 1 to 10% by weight. A liquid crystal composition containing a chiral compound in these ranges tends to have an optically isotropic liquid crystal phase.

Moreover, when using for a liquid crystal display element, it is preferable that the density | concentration of a chiral compound is adjusted and a diffraction and reflection are not recognized substantially in visible region.
The chiral compound contained in the liquid crystal composition may be one type or two or more types.

1.4 Other components The optically isotropic liquid crystal composition used in the present invention may be added with other compounds such as a polymer substance as long as it does not affect the properties of the composition. Good. The liquid crystal composition used in the present invention may contain, for example, a dichroic dye and a photochromic compound in addition to the polymer substance. Examples of dichroic dyes include merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine.

2. Monomer / Liquid Crystal Mixture and Polymer / Liquid Crystal Composite Material The monomer / liquid crystal mixture of the present invention is represented by an optically isotropic liquid crystal composition comprising an achiral liquid crystal component A and a chiral compound K, and a general formula (1). And a polymerizable monomer. Further, the optically isotropic polymer / liquid crystal composite material of the present invention indicates a material that can be used for an optical element driven in an optically isotropic liquid crystal phase, for example, the optical isotropy of the present invention. Can be prepared by polymerizing a reactive monomer / liquid crystal mixture.
In the monomer / liquid crystal mixture, the monomer content is preferably small. An increase in the amount of monomer may cause a decrease in the temperature range showing the liquid crystal phase in the liquid crystal element or an increase in driving voltage.

2.2 Polymerizable monomer The polymerizable monomer used in the present invention is a raw material of a polymer constituting the composite material, and the polymerizable monomer represented by the general formula (1) or (2) used in the present invention is A polymerizable monomer having a monofunctional single ring structure, in particular, a polymerizable monomer having a ring structure that is an aromatic ring has higher compatibility than a monomer having no ring structure. The monomer / liquid crystal mixture containing the polymerizable monomer represented by the general formula (1) or (2) used in the present invention has a uniform blue phase in a relatively wide temperature range with a smaller amount of monomer addition than conventional. Is expressed.

式（１）中、
Ｒ^ａは水素、ハロゲン、直鎖状または分岐状の炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよいが、２つの連続する−ＣＨ_２−が−Ｏ−で置き換えられることはなく、このアルキル中の任意の水素はハロゲンで置き換えられてもよい；
Ｒ^ｂは単結合、または直鎖状または分岐状の炭素数１〜３０のアルキレンであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよいが、２つの連続する−ＣＨ_２−が−Ｏ−で置き換えられることはなく、このアルキル中の任意の水素はハロゲンで置き換えられてもよく；
環Ａ^１は１，４−フェニレン、ナフタレン−２，６−ジイル、１，４−シクロヘキセニレン、１，４−ビシクロ［２，２，２］オクチレンであり、これらの環中の任意の水素がメチル基またはハロゲンで置き換えられてもよく、環中の任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、環中の任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく；
Ｘ^１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または単結合であり；
Ｐ^１は、下記の式（Ｍ３−１）〜（Ｍ３−７）のいずれかを表す。 2.2.1 Monofunctional Monomer As the polymerizable monomer used in the present invention, a compound represented by the general formula (1) which is a monofunctional monofunctional monomer having no mesogen moiety can be given.

In formula (1),
R ^a is hydrogen, halogen, linear or branched alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH ═CH— or —C≡C— may be replaced, but two consecutive —CH ₂ — are not replaced by —O—, and any hydrogen in the alkyl may be replaced by halogen. Good;
R ^b is a single bond or a linear or branched alkylene having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH ═CH— or —C≡C— may be replaced, but two consecutive —CH ₂ — are not replaced by —O—, and any hydrogen in the alkyl may be replaced by halogen. Often;
Ring ^{A 1} is 1,4-phenylene, naphthalene-2,6-diyl, 1,4-cyclohexenylene, 1,4-bicyclo [2,2,2] octylene, any hydrogen in these rings May be replaced with a methyl group or halogen, any —CH ₂ — in the ring may be replaced with —O—, and any —CH═ in the ring may be replaced with —N═. ;
X ¹ is —O—, —CO—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, or a single bond;
P ¹ represents any of the following formulas (M3-1) to (M3-7).

一般式（１）で表される単官能性モノマーとして好ましいものとして、一般式（２）で表される化合物を挙げることができる。

式（２）中、
Ｒ^ａは、直鎖状または分岐状の炭素数１〜３０のアルキル、炭素数２〜３０のアルケニル、または炭素数１〜３０のアルコキシであり、このアルキル中の任意の水素はハロゲンで置き換えられてもよく；
Ｒ^ｂは単結合、直鎖状または分岐状の炭素数１〜３０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい、このアルキレン中の任意の水素はハロゲンで置き換えられてもよく；
Ｘ^１は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または単結合であり；
Ｑ^１、Ｑ^２、Ｑ^３、およびＱ^４はそれぞれ独立に水素、フッ素、塩素、またはメチル基であり；
Ｒ^ｄは水素またはメチルであり、Ｐ^１は式（Ｍ３−３）または（Ｍ３−７）を表す。
これらの単官能性モノマーの好ましい例として、式（２−１）〜（２−３）で表される化合物が挙げられる。

式（２−１）〜（２−３）中、Ｒ^ａは、直鎖状または分岐状の炭素数１〜３０のアルキル、または炭素数２〜３０のアルケニルである。
Ｒ^ａは直鎖状のアルキルであるとき、化合物の粘性が低い。Ｒ^ａは分岐状のアルキルであるとき、化合物の特徴は分岐位置に依存するが、２位、３位で分岐した融点が低い。Ｒ^ａはアルケニルであるとき、化合物の融点が低く相溶性が良い。
好ましいＲ^ａは、直鎖状または分岐状の炭素数１〜２０のアルキル、炭素数２〜２０のアルケニルである。
Ｒ^ｂは直鎖状または分岐状の炭素数１〜３０のアルキレンである。
Ｒ^ｂは直鎖状のアルキレンであるとき、化合物の粘性が低い。Ｒ^ｂは分岐状のアルキレンであるとき、化合物の特徴は分岐位置に依存するが、２位、３位で分岐した化合物は融点が低い。好ましいＲ^ｂは、直鎖状または分岐状の炭素数１〜２０のアルキルである。
Ｑ^１、Ｑ^２、Ｑ^３、およびＱ^４はそれぞれ独立に水素、フッ素、塩素、またはメチル基である。
Ｑ^１、Ｑ^２、Ｑ^３、およびＱ^４は、水素、フッ素またはメチル基であるとき化学的に安定であり、特に好ましい。
Ｒ^ｄは水素またはメチルである。

Preferable examples of the monofunctional monomer represented by the general formula (1) include a compound represented by the general formula (2).

In formula (2),
R ^a is linear or branched alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, or alkoxy having 1 to 30 carbon atoms, and any hydrogen in the alkyl is replaced by halogen. May be;
R ^b is a single bond, linear or branched alkylene having 1 to 30 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —CH═CH— or —C≡C—. Any hydrogen in the alkylene may be replaced with a halogen;
X ¹ is —O—, —CO—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ — or a single bond;
Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently a hydrogen, fluorine, chlorine, or methyl group;
R ^d is hydrogen or methyl, and P ¹ represents the formula (M3-3) or (M3-7).
Preferable examples of these monofunctional monomers include compounds represented by formulas (2-1) to (2-3).

In formulas (2-1) to (2-3), R ^a is linear or branched alkyl having 1 to 30 carbon atoms or alkenyl having 2 to 30 carbon atoms.
When R ^a is linear alkyl, the viscosity of the compound is low. When R ^a is branched alkyl, the characteristics of the compound depend on the branch position, but the melting point branched at the 2-position and 3-position is low. When ^Ra is alkenyl, the compound has a low melting point and good compatibility.
Preferred R ^a is linear or branched alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms.
R ^b is a linear or branched alkylene having 1 to 30 carbon atoms.
When R ^b is linear alkylene, the viscosity of the compound is low. When R ^b is branched alkylene, the characteristics of the compound depend on the branch position, but the compound branched at the 2-position and 3-position has a low melting point. Preferred R ^b is linear or branched alkyl having 1 to 20 carbon atoms.
Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently hydrogen, fluorine, chlorine, or a methyl group.
Q ¹ , Q ² , Q ³ , and Q ⁴ are particularly preferable because they are chemically stable when they are hydrogen, fluorine, or a methyl group.
R ^d is hydrogen or methyl.

式（１）で表される化合物を合成する方法は複数あり、市販の試薬から適宜、本明細書実施例や文献、書籍を参考にして合成することが可能である。下記にその一例として反応スキーム（スキーム１〜３）を示す。化合物（１）の合成方法は、ここで示す合成例に限定するものではない。 Preferred examples of the compound represented by formula (1) below include compounds (2-1-1) to (2-1-38), (2-2-1) to (2-2-14), ( 2-3-1) to (2-3-16) and (2-4-1) to (2-4-22) are shown.

There are a plurality of methods for synthesizing the compound represented by the formula (1), and it can be appropriately synthesized from commercially available reagents with reference to Examples, literatures and books in this specification. A reaction scheme (Schemes 1 to 3) is shown below as an example. The synthesis method of compound (1) is not limited to the synthesis examples shown here.

  <Scheme 1> Preparation of Compound (2-1)

フェノール誘導体とハロゲンの誘導体に塩基を用いてエーテル化を行い、得られた化合物に適切なカルボン酸クロライドを作用させて目的物を得る。
式中、Ｒ^ａは式（２−１）で与えられる意味を有し、ｎは１〜３０である。

Etherification is performed on a phenol derivative and a halogen derivative using a base, and an appropriate carboxylic acid chloride is allowed to act on the obtained compound to obtain a target product.
Wherein, ^{R a} has the meaning given in equation (2-1), n is 1 to 30.

ベンズアルデヒドの誘導体に対応するwittig試薬を作用させて得られた化合物に、パラジウムなどの触媒を用いて水素還元する。次いで、保護基を脱保護反応させて得られたアルデヒドの誘導体を、ＬＡＨなどの還元剤を作用させてアルコール誘導体を得る。最後にこのアルコール誘導体と適切なカルボン酸クロライドと反応させて目的物を得ることができる。
式中、Ｒ^ａは式（２−２）で与えられる意味を有し、ｎは１〜３０である。
<Scheme 2> Preparation of Compound (2-2)

A compound obtained by reacting a wittig reagent corresponding to a derivative of benzaldehyde is reduced with hydrogen using a catalyst such as palladium. Next, an aldehyde derivative obtained by deprotecting the protecting group is reacted with a reducing agent such as LAH to obtain an alcohol derivative. Finally, this alcohol derivative is reacted with an appropriate carboxylic acid chloride to obtain the desired product.
Wherein, ^{R a} has the meaning given in equation (2-2), n is 1 to 30.

カルボン酸誘導体とハロゲン誘導体をエステル化して得られた化合物に、適切なカルボン酸と塩基を用いて反応させることにより目的物を得る。
式中、Ｒ^ａは式（２−３）で与えられる意味を有し、ｎは１〜３０である。 <Scheme 3> Preparation of Compound (2-3)

A compound obtained by esterifying a carboxylic acid derivative and a halogen derivative is reacted with an appropriate carboxylic acid and a base to obtain a target product.
In the formula, R ^a has the meaning given by Formula (2-3), and n is 1 to 30.

  About the said monomer, as a suitable example of a compound represented by Formula (2-1), the suitable example of a compound represented by Formula (2-1-1)-(2-1-10), Formula (2-2). As formulas (2-2-1) to (2-2-10) and as preferred examples of the compounds represented by formula (2-3), formulas (2-3-1) to (2-3-10) Each can be mentioned.

In the present invention, in addition to the polymerizable monomer represented by the general formula (1) or (2), other polymerizable monomers can also be used. As the polymerizable monomer other than the polymerizable monomer represented by the general formula (1) or (2), for example, a low molecular weight monomer, a macromonomer, and an oligomer can be used. In the present specification, the high molecular weight raw material monomer is used to include low molecular weight monomers, macromonomers, oligomers, and the like.
The polymerizable monomer is preferably used in combination with a polyfunctional monomer having two or more polymerizable functional groups and a monofunctional monomer having one polymerizable functional group. A polyfunctional monomer tends to form a three-dimensional crosslinked structure when it is made into a polymer. On the other hand, the monofunctional monomer has good compatibility with the liquid crystal composition.
Here, the monofunctional monomer does not mean that the monofunctional single monomer is used alone. It is also preferable to use in combination with a monomer having no ring structure such as alkyl acrylate or alkyl methacrylate, if necessary to improve the properties of the polymer / liquid crystal composite material obtained by polymerization.
The polymerizable functional group is not particularly limited, and an acrylic group, a methacryl group, a glycidyl group, an epoxy group, an oxetanyl group, a vinyl group, and the like can be raised, but an acrylic group and a methacryl group are preferable from the viewpoint of polymerization rate. When a monomer having two or more polymerizable functional groups in the polymer raw material monomer is contained in an amount of 10% by weight or more, high transparency and isotropy are easily exhibited in the composite material of the present invention. This is preferable.
In order to obtain a suitable composite material, it is also preferable to add a polymer having a mesogen moiety combined with a bonding group or a ring structure. A raw material monomer having a mesogen moiety is used as a polymer raw material monomer. It can be used for parts.

2.2.2 Bifunctional monomer In the polymerizable monomer other than the polymerizable monomer represented by the general formula (1) or (2), among the polyfunctional monomers, the bifunctional monomer is represented by the following formula (M2). The compound represented by these can be mentioned.

^{R C -Y M - (A M} -Z M) m1 -A M -Y M -R C (M2)

In formula (M2), R ^C each independently represents a polymerizable group of groups (M3-1) to (M3-7).

In formula (M2), R ^C each independently represents a polymerizable group of groups (M3-1) to (M3-7).

Here, R ^d in the group (M3-1) to the group (M3-7) is each independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen is replaced with halogen. May be. Preferred R ^d is hydrogen, halogen and methyl. Particularly preferred R ^d is hydrogen, fluorine and methyl.
The group (M3-2), the group (M3-3), the group (M3-4), and the group (M3-7) are preferably polymerized by radical polymerization. The group (M3-1), the group (M3-5) and the group (M3-6) are preferably polymerized by cationic polymerization. Since both are living polymerizations, the polymerization starts when a small amount of radically active species or cationically active species are generated in the reaction system. A polymerization initiator can be used for the purpose of accelerating the generation of these active species. For example, light or heat can be used to generate these active species.

In formula (M2), A ^M is each independently an aromatic or non-aromatic 5-membered ring, 6-membered ring, or condensed ring having 9 to 20 carbon atoms, and —CH ₂ — in the ring Is —O—, —S—, —NH—, or —NCH ₃ —, wherein —CH═ in the ring may be replaced by —N═, the hydrogen atom on the ring is halogen, and 1 to 5 carbon atoms Or an alkyl halide. Specific examples of preferred ^{A M} are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene -2, 7-diyl or bicyclo [2.2.2] octane-1,4-diyl, and in these rings, any —CH ₂ — may be replaced by —O—, and any —CH═ is -N = may be substituted, and in these rings, any hydrogen may be substituted with halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms.
In consideration of the stability of the compound, —CH ₂ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other than —CH ₂ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other Is preferred. The same applies to sulfur.

Among these, particularly preferred ^{A M,} 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4 -Phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2 , 3-bis (trifluoromethyl) -1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7- Diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, and pyrimidine-2,5-diyl. The steric configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis.
Since 2-fluoro-1,4-phenylene is structurally identical to 3-fluoro-1,4-phenylene, the latter was not exemplified. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

In formulas (M1) and (M2), Y ^M is each independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — is —O—, —S—, -CH = CH-, -C≡C-, -COO-, or -OCO- may be substituted. Preferred ^{Y M} is a single _{bond, - (CH 2) m2 -} , - O (CH 2) m2 -, and - in (CH ₂₎ (in the formula, m2 is an integer of 1 to 20) _{m @ 2} O- is there. Particularly preferred Y ^M is a single bond, — (CH ₂ ) _n —, —O (CH ₂ ) _{m 2} —, and — (CH ₂ ) _{m 2} O— (wherein _{m 2} is an integer of 1 to 10). It is. In consideration of the stability of the compound, ^-Y M -R ^a and ^-Y M -R ^b are, -O-O in their groups -, - O-S -, - S-O-, or -S It is preferable not to have -S-.

In formula (M2), Z ^M each independently represents a single bond, — (CH ₂ ) _{m 3} —, —O (CH ₂ ) _{m 3} —, — (CH ₂ ) _{m 3} O—, —O (CH ₂ ) _{m 3} O -, - CH = CH - , - C≡C -, - COO -, - OCO -, - (CF 2) 2 -, - (CH 2) 2 -COO -, - OCO- (CH 2) 2 - , —CH═CH—COO—, —OCO—CH═CH—, —C≡C—COO—, —OCO—C≡C—, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH—C≡C—, —OCF ₂ — (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CF ₂ O—, —OCF ₂ — or —CF ₂ O— (wherein m3 is an integer of 1 to 20).

Preferred Z ^M is a single bond, — (CH ₂ ) _{m 3} —, —O (CH ₂ ) _{m 3} —, — (CH ₂ ) _{m 3} O—, —CH═CH—, —C≡C—, —COO—, — _{OCO -, - (CH 2)} 2 -COO -, - OCO- (CH 2) 2 -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, and _-CF 2 O- It is.

In formula (M2), m1 is an integer of 1-6. Preferred m1 is an integer of 1 to 3. When m1 is 1, it is a bicyclic compound having two rings such as a 6-membered ring. When m1 is 2 or 3, they are tricyclic and tetracyclic compounds, respectively. For example, when m1 is 1, two A ^M may be may be the same or different. For example, when m1 is 2, three A ^M (or two Z ^M ) may be the same or different. The same applies when m1 is 3-6. The same applies to R ^C , R ^d , Z ^M , A ^M and Y ^M.

The compound represented by the formula (M2) can be preferably used because it has the same characteristics even when it contains more isotopes such as ² H (deuterium) and ¹³ C than the natural abundance.

More preferred examples of the compound (M2) are compounds represented by (M2-1) to (M2-27). In these compounds, the meanings of R ^C , R ^d , Z ^M , A ^M , and Y ^M are the same as those of formula (M2) described in the embodiments of the present invention.

The following partial structures of the compounds (M2-1) to (M2-27) will be described. The partial structure (a1) represents 1,4-phenylene in which arbitrary hydrogen is replaced by fluorine. The partial structure (a2) represents 1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine. The partial structure (a3) represents 1,4-phenylene in which arbitrary hydrogen may be replaced by either fluorine or methyl. The partial structure (a4) represents fluorene in which the hydrogen at the 9-position may be replaced with methyl.

Among the above liquid crystal monomer groups, formula (M2-15-1) is particularly preferable. (In the formula, Y ¹ is an acrylate group or a methacrylate group, and n is an integer of 1 to 20.)

2.2.3 Other Monomers A polymerizable compound other than the monocyclic monofunctional monomer (1) and the bifunctional monomer (M2) described above can be used as necessary.

(1) Multifunctional monomer (trifunctional or higher)
For the purpose of optimizing the optical isotropy of the polymer / liquid crystal composite material of the present invention, a monomer having a mesogenic moiety and having three or more polymerizable functional groups may be used. As the monomer having a mesogenic moiety and having three or more polymerizable functional groups, known compounds can be suitably used. For example, (M4-1) to (M4-3), and more specific examples include Examples thereof include compounds described in JP 2000-327632 A, JP 2004-182949 A, and JP 2004-59777 A. However, in (M4-1) to (M4-3), R ^C , Z ^M , Y ^M , and (F) have the same meaning as described above.

(2) Polymerizable monomer having no ring structure For the purpose of optimizing the optical isotropy of the polymer / liquid crystal composite material of the present invention, as a monomer having a polymerizable functional group having no ring structure. Examples of the monomer having a linear or branched acrylate having 1 to 30 carbon atoms, a linear or branched diacrylate having 1 to 30 carbon atoms, and three or more polymerizable functional groups include glycerol propoxylate (1PO / OH ) Triacrylate, pentaerythritol / propoxylate / triacrylate, pentaerythritol / triacrylate, trimethylolpropane / ethoxylate / triacrylate, trimethylolpropane / propoxylate / triacrylate, trimethylolpropane / triacrylate, di (trimethylol) Propane) Tetraacryl Examples thereof include, but are not limited to, rate, pentaerythritol tetraacrylate, di (pentaerythritol) pentaacrylate, di (pentaerythritol) hexaacrylate, and trimethylolpropane triacrylate.

2.2 Polymerization conditions for producing polymer / liquid crystal composite material The optically isotropic polymer / liquid crystal composite material of the present invention is a composite material containing both a liquid crystal material and a polymer compound. Although not particularly limited, the polymer may be phase-separated from the liquid crystal material in a state where part or all of the polymer is not dissolved in the liquid crystal material. The polymer / liquid crystal composite material of the present invention can be produced by mixing an optically isotropic liquid crystal composition and a polymer obtained by polymerizing in advance, but it has a low molecular weight as a polymer material. And a monomer, macromonomer, oligomer, etc. (hereinafter collectively referred to as “monomer etc.”) and an optically isotropic liquid crystal composition, and then a polymerization reaction is performed in the mixture. Is preferred.
The polymerization in the mixture is preferably performed in the non-liquid crystal isotropic phase or the optically isotropic liquid crystal phase. That is, the polymerization temperature is preferably a temperature at which the polymer / liquid crystal composite material exhibits high transparency and isotropic properties. More preferably, the polymerization is terminated at a temperature at which the mixture of the monomer and the liquid crystal material develops the non-liquid crystal isotropic phase or the blue phase, and at the non-liquid crystal isotropic phase or the optically isotropic liquid crystal phase. That is, after polymerization, the polymer / liquid crystal composite material is preferably set to a temperature that does not substantially scatter light on the longer wavelength side than visible light and develops an optically isotropic state.

2.3 Polymerization initiator The polymerization reaction in the production of the polymer constituting the composite material of the present invention is not particularly limited, and for example, photoradical polymerization, thermal radical polymerization, photocationic polymerization, and the like are performed.

  Examples of radical photopolymerization initiators that can be used in radical photopolymerization include DAROCUR 1173 and 4265 (both trade names, BASF Japan Ltd.), Irgacure 184, 369, 500, 651, and 784. , 819, 907, 1300, 1700, 1800, 1850, and 2959 (all trade names, BASF Japan Ltd.), and the like.

  Examples of preferred initiators for thermal radical polymerization that can be used in thermal radical polymerization are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate , T-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbox Nitrile (ACN) and the like.

  Examples of the cationic photopolymerization initiator that can be used in the cationic photopolymerization include diaryliodonium salts (hereinafter referred to as “DAS”), triarylsulfonium salts (hereinafter referred to as “TAS”), and the like.

  DAS includes diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra (pentafluorophenyl) ) Borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxypheny Phenyl iodonium trifluoroacetate, 4-methoxyphenyl phenyl iodonium -p- toluenesulfonate and the like.

  DAS can be made highly sensitive by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and rubrene.

  TAS includes triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane Sulfonar , 4-methoxyphenyl diphenyl sulfonium trifluoroacetate, 4-methoxyphenyl diphenyl sulfonium -p- toluenesulfonate and the like.

  Examples of specific trade names of the photocationic polymerization initiator include Cyracure UVI-6990, Cyracure UVI-6974, Cyracure UVI-6922 (trade names, UCC Corporation, respectively), Adekaoptomer SP-150, SP-152, SP-170, SP-172 (each trade name, ADEKA Corporation), Rhodorsil Photoinitiator 2074 (trade name, Rhodia Japan Co., Ltd.), Irgacure (IRGACURE) 250 (trade name, BASF Japan Co., Ltd.) ), UV-9380C (trade name, GE Toshiba Silicone Co., Ltd.).

2.4 Curing Agent, etc. In the production of the polymer constituting the composite material of the present invention, in addition to the monomer and the polymerization initiator, one or more other suitable components such as a curing agent, a catalyst, etc. , Stabilizers and the like may be added.

  As the curing agent, conventionally known latent curing agents that are usually used as curing agents for epoxy resins can be used. Examples of the latent epoxy resin curing agent include amine curing agents, novolak resin curing agents, imidazole curing agents, and acid anhydride curing agents. Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, and isophoronediamine. , Cycloaliphatic polyamines such as 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, aromatics such as diaminodiphenylmethane, diaminodiphenylethane, metaphenylenediamine Group polyamines and the like.

  Examples of novolak resin-based curing agents include phenol novolac resins and bisphenol novolac resins. Examples of the imidazole curing agent include 2-methylimidazole, 2-ethylhexylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like.

  Examples of acid anhydride curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride and the like can be mentioned.

  Moreover, you may further use the hardening accelerator for accelerating the hardening reaction of the polymeric compound which has glycidyl, an epoxy, and oxetanyl, and a hardening | curing agent. Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 2-ethyl-4-methyl. Imidazoles such as imidazole, organophosphorus compounds such as triphenylphosphine, quaternary phosphonium salts such as tetraphenylphosphonium bromide, 1,8-diazabicyclo [5.4.0] undecene-7, and organic acid salts thereof Examples include diazabicycloalkenes, quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide, and boron compounds such as boron trifluoride and triphenylborate. These curing accelerators can be used alone or in admixture of two or more.

  Also, for example, a stabilizer is preferably added to prevent undesired polymerization during storage. All compounds known to those skilled in the art can be used as stabilizers. Representative examples of the stabilizer include 4-ethoxyphenol, hydroquinone, butylated hydroxytoluene (BHT) and the like.

  The optically isotropic polymer / liquid crystal composite material according to a preferred embodiment of the present invention can exhibit an optically isotropic liquid crystal phase in a wide temperature range. Further, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention has an extremely fast response speed. Moreover, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention can be suitably used for an optical element such as a display element based on these effects.

2.5 Content of liquid crystal composition, etc. The content of the liquid crystal composition in the polymer / liquid crystal composite material of the present invention is as high as possible as long as the composite material can exhibit isotropic properties. Preferably there is. This is because the electric birefringence value (Kerr coefficient) of the composite material of the present invention increases as the content of the liquid crystal composition is higher.

  In the polymer / liquid crystal composite material of the present invention, the content of the liquid crystal composition is preferably 60 to 99% by weight, more preferably 60 to 95% by weight, particularly 75 to 95% by weight based on the composite material. preferable. The content of the polymer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and particularly preferably 3 to 25% by weight with respect to the composite material.

3 Liquid Crystal Element Optically isotropic including the monomer / liquid crystal mixture or polymer / liquid crystal composite material of the present invention (hereinafter, the monomer / liquid crystal mixture and polymer / liquid crystal composite material may be collectively referred to as “liquid crystal medium”) Optical element driven in a liquid crystal phase.
As an example of the structure of the liquid crystal display element, as shown in FIG. 1, the electrodes of the comb-shaped electrode substrate are an electrode 1 extending in the right direction from the left connection electrode portion and an electrode extending in the left direction from the right connection electrode portion. A structure in which 2 are alternately arranged can be exemplified. When there is a potential difference between the electrode 1 and the electrode 2, it is possible to provide a state in which an electric field exists in two directions, an upper direction and a lower direction, on the comb electrode substrate as shown in FIG.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

In the examples of the present specification, I is a non-liquid crystal isotropic phase, N is a nematic phase, N ^* is a chiral nematic phase, BP is a blue phase, and BPX is optically isotropic where diffracted light of two or more colors is not observed. Represents the liquid crystal phase. In the present specification, the IN phase transition point is sometimes referred to as the NI point. The IN ^* transition point is sometimes referred to as the N ^* -I point. The I-BP phase transition point is sometimes referred to as a BP-I point.

４−ペンチルフェノール（２４．３ｇ，１４８．２ｍｍｏｌ）をＤＭＦ（１００ｍｌ）に溶解させ、８−クロロオクタノール（２４．４ｇ，１４８．２ｍｍｏｌ）、炭酸カリウム（４１．０ｇ，２９６．４ｍｍｏｌ）を加え窒素雰囲気下８０℃で３０時間加熱撹拌した。反応終了後水を加え、さらに溶液を酸性にした後トルエンを加えて抽出した。水、飽和塩化ナトリウム水溶液で洗浄した後、無水硫酸マグネシウムにて乾燥し、溶媒を減圧濃縮した。シリカゲルカラムクロマトグラフィーで精製し、化合物（Ｓ−０１）を得た（２８．３ｇ，６５％）。 A synthesis example of a monofunctional monomer used in the present invention is shown below.
Example 1: Synthesis of acrylic acid-8- (4-pentylphenoxy) -octyl ester

4-Pentylphenol (24.3 g, 148.2 mmol) is dissolved in DMF (100 ml), and 8-chlorooctanol (24.4 g, 148.2 mmol) and potassium carbonate (41.0 g, 296.4 mmol) are added and nitrogen is added. The mixture was heated and stirred at 80 ° C. for 30 hours in an atmosphere. After completion of the reaction, water was added, the solution was further acidified, and toluene was added for extraction. The extract was washed with water and a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The product was purified by silica gel column chromatography to obtain compound (S-01) (28.3 g, 65%).

Compound (S-01) (15.0 g, 51.3 mmol) was dissolved in THF (130 ml), and triethylamine (8.6 ml, 61.6 mmol) was added. After cooling to 0 ° C., acrylic acid chloride (5.0 ml, 61.6 mmol) was added dropwise under a nitrogen atmosphere. The reaction was returned to room temperature and allowed to stir overnight. After the reaction was complete, it was quenched by pouring into water and extracted with ethyl acetate. The extract was washed with water, a saturated aqueous sodium hydrogen carbonate solution, and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography and crystallization gave the desired product as a colorless liquid. (13.1 g, 74% yield)
¹ H-NMR (CDCl ₃ ): δ (ppm); 0.88 (t, 3H), 1.27-1.47 (m, 12H), 1.54-1.60 (m, 2H), 1 .64-1.70 (m, 2H), 1.73-1.79 (m, 2H), 2.53 (t, 2H), 3.92 (t, 2H), 4.15 (t, 2H) ), 5.81 (dd, 1H), 6.12 (dd, 1H), 6.40 (dd, 1H), 6.79-6.82 (m, 2H), 7.07-7.08 ( m, 2H).

化合物（Ｓ−０１）（６．０ｇ，２０．５ｍｍｏｌ）を出発原料として、アクリル酸クロリドの代わりにメタクリル酸クロリド（２．４ｍｌ，２４．６ｍｍｏｌ）を用いて例１と同様の方法で合成を行い。無色の液体である目的物を得た。（３．４ｇ，収率４６％）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ（ｐｐｍ）；０．８８（ｔ，３Ｈ）、１．２６−１．４６（ｍ，１２Ｈ）、１．５３−１．６０（ｍ，２Ｈ）、１．６４−１．７０（ｍ，２Ｈ）、１．７３−１．７９（ｍ，２Ｈ）、１．９４（ｓ，３Ｈ）、２．５３（ｔ，２Ｈ）、３．９２（ｔ，２Ｈ）、４．１４（ｔ，２Ｈ）、５．５３−５．５４（ｍ，１Ｈ）、６．１０（ｓ，１Ｈ）、６．７９−６．８２（ｍ，２Ｈ）、７．０６−７．０８（ｍ，２Ｈ）． Example 2: Methacrylic acid-8- (4-pentylphenoxy) -octyl ester

The compound (S-01) (6.0 g, 20.5 mmol) was used as a starting material, and methacrylic acid chloride (2.4 ml, 24.6 mmol) was used instead of acrylic acid chloride in the same manner as in Example 1. Done. The target product was obtained as a colorless liquid. (3.4 g, yield 46%)
¹ H-NMR (CDCl ₃ ): δ (ppm); 0.88 (t, 3H), 1.26 to 1.46 (m, 12H), 1.53-1.60 (m, 2H), 1 .64-1.70 (m, 2H), 1.73-1.79 (m, 2H), 1.94 (s, 3H), 2.53 (t, 2H), 3.92 (t, 2H) ), 4.14 (t, 2H), 5.53-5.54 (m, 1H), 6.10 (s, 1H), 6.79-6.82 (m, 2H), 7.06- 7.08 (m, 2H).

４−プロピルフェノール（１０．０ｇ，７３．４ｍｍｏｌ）をトルエン（３００ｍｌ）に溶解させ、４−ブロモブタノール（８０ｗｔ％，２１．１ｇ，１１０．１ｍｍｏｌ）、トリフェニルホスフィン（２８．９ｇ，１１０．１ｍｍｏｌ）を加え窒素雰囲気下で０℃に冷却した。アゾジカルボン酸ジエチルの４０ｗｔ％トルエン溶液（４８．０ｇ，１１０．１ｍｍｏｌ）を滴下し、終夜撹拌を行った。反応終了後。溶媒を留去し、ヘプタンを加えてろ過を行った。ろ液を濃縮し、シリカゲルカラムクロマトグラフィーで精製し、無色の液体として化合物（Ｓ−０２）を得た（１６．９ｇ，８５％）。
化合物（Ｓ−０２）（７．０ｇ，２２．７ｍｍｏｌ）をＴＨＦ（１４０ｍｌ）に溶解させ、炭酸水素カリウム（９．０９ｇ，９０．９ｍｍｏｌ）、ヨウ化テトラブチルアンモニム（１．６８ｇ，４．５ｍｍｏｌ）、ジブチルヒドロキシトルエン（０．４０ｇ，１．８ｍｍｏｌ）を加えて窒素雰囲気下で加熱還流させた。反応終了後、水に注いでクエンチし、ジエチルエーテルにて抽出した。水、飽和塩化ナトリウム水溶液にて洗浄し、無水硫酸マグネシウムで乾燥させた。減圧濃縮し、シリカゲルカラムクロマトグラフィーおよび晶析によって精製し、無色の液体である目的物を得た。（３．１ｇ，収率４６％）

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ（ｐｐｍ）；０．９２（ｔ，３Ｈ）、１．５６−１．６４（ｍ，２Ｈ）、１．８６−１．８８（ｍ，４Ｈ）、２．５２（ｔ，２Ｈ）、３．９５−４．００（ｍ，２Ｈ）、４．２１−４．２４（ｍ，２Ｈ）、５．８２（ｄｄ，１Ｈ）、６．１２（ｄｄ，１Ｈ）、６．４０（ｄｄ，１Ｈ）、６．７９−６．８２（ｍ，２Ｈ）、７．０７−７．０８（ｍ，２Ｈ）． Example 3: Synthesis of acrylic acid-4- (4-propylphenoxy) -butyl ester

4-Propylphenol (10.0 g, 73.4 mmol) was dissolved in toluene (300 ml), 4-bromobutanol (80 wt%, 21.1 g, 110.1 mmol), triphenylphosphine (28.9 g, 110.1 mmol). ) And cooled to 0 ° C. under a nitrogen atmosphere. A 40 wt% toluene solution of diethyl azodicarboxylate (48.0 g, 110.1 mmol) was added dropwise and stirred overnight. After the reaction is complete. The solvent was distilled off, and heptane was added for filtration. The filtrate was concentrated and purified by silica gel column chromatography to obtain compound (S-02) as a colorless liquid (16.9 g, 85%).
Compound (S-02) (7.0 g, 22.7 mmol) was dissolved in THF (140 ml), potassium hydrogen carbonate (9.09 g, 90.9 mmol), tetrabutylammonium iodide (1.68 g, 4. 5 mmol) and dibutylhydroxytoluene (0.40 g, 1.8 mmol) were added and heated to reflux under a nitrogen atmosphere. After completion of the reaction, the reaction was quenched by pouring into water and extracted with diethyl ether. The extract was washed with water and a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography and crystallization gave the desired product as a colorless liquid. (3.1 g, yield 46%)

¹ H-NMR (CDCl ₃ ): δ (ppm); 0.92 (t, 3H), 1.56-1.64 (m, 2H), 1.86-1.88 (m, 4H), 2 .52 (t, 2H), 3.95-4.00 (m, 2H), 4.21-4.24 (m, 2H), 5.82 (dd, 1H), 6.12 (dd, 1H) ), 6.40 (dd, 1H), 6.79-6.82 (m, 2H), 7.07-7.08 (m, 2H).

  In the present invention, the characteristic value of the liquid crystal composition can be measured according to the following method. Many of them are the methods described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof. No TFT was attached to the TN device used for measurement.

  Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

  Minimum temperature of nematic phase (TC; ° C.): A sample having a nematic phase is stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase is observed did. For example, when the sample remains in a nematic phase at −20 ° C. and changes to a crystal (or smectic phase) at −30 ° C., TC is described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

  Optically isotropic liquid crystal phase transition temperature: Place the sample on the hot plate of a melting point measurement device equipped with a polarizing microscope, and in the crossed Nicols state, the sample was first heated to a temperature at which the sample becomes an isotropic liquid crystal phase Thereafter, the temperature was lowered at a rate of 1 ° C./min, and a completely chiral nematic phase or an optically isotropic liquid crystal phase appeared. The temperature at which the phase transition in the temperature lowering process was measured, then the temperature was increased at a rate of 1 ° C./min, and the temperature at which the phase transition in the temperature rising process was measured. In the present invention, unless otherwise specified, the phase transition temperature in the temperature raising process is defined as the phase transition temperature. In the optically isotropic liquid crystal phase, when it was difficult to distinguish the phase transition temperature in the dark field under crossed Nicols, the phase transition temperature was measured by shifting the polarizing plate by 1 to 10 ° from the crossed Nicols state.

  Viscosity (η; measured at 20 ° C .; mPa · s): An E-type viscometer was used for measurement.

Rotational viscosity (γ1; measured at 25 ° C .; mPa · s):
1) Sample having positive dielectric anisotropy: Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. The voltage was applied to the TN device in steps of 0.5 volts in the range of 16 to 19.5 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of dielectric anisotropy necessary for this calculation was obtained by the following dielectric anisotropy measurement method using the element used for the measurement of the rotational viscosity.

2) Sample with negative dielectric anisotropy: Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt in the range of 30 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. As the dielectric anisotropy necessary for this calculation, a value measured by the following dielectric anisotropy was used.

  Refractive index anisotropy (Δn; measured at 25 ° C.): The measurement was performed with an Abbe refractometer using light with a wavelength of 589 nm and a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of refractive index anisotropy was calculated from the equation: Δn = n∥−n⊥. When the sample was a composition, the refractive index anisotropy was measured by this method.

Dielectric anisotropy (Δε; measured at 25 ° C.):
1) Composition having a positive dielectric anisotropy: A sample was placed in a liquid crystal cell in which the distance (gap) between two glass substrates was about 9 μm and the twist angle was 80 degrees. 20 volts was applied to the cell, and the dielectric constant (ε 率) in the major axis direction of the liquid crystal molecules was measured. 0.5 V was applied, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

2) Composition having a negative dielectric anisotropy: A sample was placed in a liquid crystal cell treated in a homeotropic alignment, and 0.5 volt was applied to measure the dielectric constant (ε ボ ル ト). A sample was put in a liquid crystal cell treated to homogeneous alignment, and a dielectric constant (ε⊥) was measured by applying 0.5 volts. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

Threshold voltage (Vth; measured at 25 ° C .; V):
1) A composition having a positive dielectric anisotropy: a normally white mode (normally white mode) in which a distance (gap) between two glass substrates is (0.5 / Δn) μm and a twist angle is 80 degrees. A sample was put in a liquid crystal display element in white mode). Δn is a value of refractive index anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.

2) Composition having a negative dielectric anisotropy: For a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 μm and is processed in a homeotropic alignment. A sample was placed. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.

  Voltage holding ratio (VHR; measured at 25 ° C .;%): The TN device used for measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 6 μm. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample. The TN device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is an area when it is not attenuated. The voltage holding ratio is a percentage of the area A with respect to the area B.

  Helical pitch (measured at 20 ° C .; μm): Kano's wedge cell method was used to measure the helical pitch. A sample was injected into a Kano wedge-shaped cell, and the distance (a; unit: μm) between disclination lines observed from the cell was measured. The helical pitch (P) was calculated from the formula P = 2 · a · tan θ. θ is the angle between the two glass plates in the wedge-shaped cell.

Alternatively, the pitch length was measured using selective reflection (Liquid Crystal Manual 196 (issued in 2000, Maruzen). For the selective reflection wavelength λ, the relational expression <n> p / λ = 1 holds, where <n > Represents the average refractive index and is given by the following formula: <n> = {(n 2 + n 2) / 2} 1/2 The selective reflection wavelength is a microspectrophotometer (JEOL Ltd., trade name) MSV-350) The pitch was obtained by dividing the obtained reflection wavelength by the average refractive index.
The pitch of a cholesteric liquid crystal having a reflection wavelength in the longer wavelength region than visible light is proportional to the reciprocal of the concentration of the chiral agent in a region where the chiral agent concentration is low, so the pitch length of a liquid crystal having a selective reflection wavelength in the visible light region is increased. Several points were measured and obtained by linear extrapolation.

  The ratio (percentage) of the component or the liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound. The composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component.

この液晶組成物Ａの相転移温度（℃）はＮ ７９．７ Ｉであった。 Example 1
A liquid crystal composition NLC-A was prepared by mixing the liquid crystal compounds shown in the figure below at the following ratio.
The correspondence with the general formula is shown on the right side of the structural formula.

Liquid crystal composition NLC-A

The liquid crystal composition A had a phase transition temperature (° C.) of N 79.7 I.

Next, a liquid crystal composition composed of a liquid crystal composition NLC-A (94.7 wt%) and a chiral agent BN-H4 (2.65 wt%) and BN-H5 (2.65 wt%) represented by the following formula: CLC-A was obtained.
The liquid crystal composition CLC-A had a phase transition temperature (° C.) of N * 69.7 BP 71.4 I.

ＢＮ−Ｈ５

BN-H4 and BN-H5 are esterified from (R)-(+)-1,1′-bi (2-naphthol) and the corresponding carboxylic acid using dicyclohexylcarbodiimide (DCC). Obtained.

BN-H4

BN-H5

(Example 2)
Preparation of mixture of monomer and liquid crystal composition 89.6% by weight of liquid crystal composition CLC-A as a mixture of liquid crystal composition and monomer, acrylic acid-4- (4-propylphenoxy) -butyl ester synthesized in Example 3 (2-1-2) 6.0 wt%, 1,4-di (4- (6- (acryloyloxy) hexyloxy) benzoyloxy) -2-methylbenzene (LCA-6) 4 wt%, A liquid crystal composition MLC-A in which 0.4% by weight of 2,2′-dimethoxyphenylacetophenone was mixed as a photopolymerization initiator was prepared. The liquid crystal composition MLC-A had a phase transition temperature (° C.) of N * 45.8BP and BP44.0N *.
LCA-6

Example 3
Polymerization temperature margin after dropping About 5 mg of the liquid crystal composition MLC-A in which spacers of 10 microns were dispersed was dropped on a glass substrate at 50 ° C. and left at that temperature for 10 minutes. Then, the cell was created by bonding an opposing glass substrate. This cell was cooled from 46.3 ° C. to the polymerization temperature, and irradiated with ultraviolet light (ultraviolet light intensity 23 mWcm −2 (365 nm)) for 1 minute to carry out a polymerization reaction. The polymerization temperatures were 46.3 ° C, 45.8 ° C, 45.3 ° C, 45.1 ° C, and 44.8 ° C. When the obtained polymer / liquid crystal composite material A was observed, the polymerized at 45.1 ° C. was the entire N * phase, and the polymerized at 45.3 ° C. was the entire BP phase. In the polymer / liquid crystal composite material A obtained at all the above polymerization temperatures, the coexistence of the N * phase and the BP phase was not confirmed. That is, the polymerization temperature range in which concentration unevenness may be caused by the coexistence of the N * phase and the BP phase was less than 0.2 ° C.

(Comparative Example 1)
A liquid crystal composition MLC-B was prepared in the same manner as in Example 2 except that acrylic acid-4- (4-propylphenoxy) -butyl ester (2-1-2) was replaced with n-dodecyl acrylate. The liquid crystal composition MLC-B had a phase transition temperature (° C.) of N * 39.6 BP and BP 36.7 N *.

(Comparative Example 2)
About 5 mg of a liquid crystal composition MLC-B in which a 10-micron spacer was dispersed was dropped on a glass substrate at 50 ° C. and left at that temperature for 10 minutes. Then, the cell was created by bonding an opposing glass substrate. This cell was cooled from 40.1 ° C. to the polymerization temperature, and irradiated with ultraviolet light (ultraviolet light intensity 23 mWcm −2 (365 nm)) for 1 minute to carry out a polymerization reaction. The polymerization temperatures were 40.1 ° C, 39.6 ° C, 39.3 ° C, 39.1 ° C, 38.9 ° C and 38.6 ° C. When the obtained polymer / liquid crystal composite material B was observed, the polymerized at 38.6 ° C. was the entire N * phase, and the polymerized at 39.6 ° C. was the entire BP phase. On the other hand, in the polymer / liquid crystal composite material B obtained by polymerization at 39.3 ° C., 39.1 ° C., and 38.9 ° C., density unevenness due to the presence of both the N * phase and the BP phase was confirmed. . That is, the polymerization temperature range at which density unevenness may be caused by the coexistence of the N * phase and the BP phase was 0.4 ° C. or more and less than 1.0 ° C. at least.

Example 4
Preparation of mixture of monomer and liquid crystal composition 88.8% by weight of liquid crystal composition CLC-A as a mixture of liquid crystal composition and monomer, acrylic acid-4- (4-propylphenoxy) -butyl ester synthesized in Example 3 6.5% by weight of (2-1-2), 4.3% of 1,4-di (4- (6- (acryloyloxy) hexyloxy) benzoyloxy) -2-methylbenzene (LCA-6) %, And a liquid crystal composition MLC-A-1 containing 0.4% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator was prepared. The liquid crystal composition MLC-A-1M had a phase transition temperature (° C.) of N * 43.9 BP 45.2 I. BP was also expressed during the cooling process.

Preparation of polymer / liquid crystal composite material The liquid crystal composition MLC-A-1 was sandwiched between a non-aligned comb-shaped electrode substrate and a counter glass substrate (non-electrode provided) (cell thickness 7 μm) to obtain The resulting cell was heated to a 44.1 ° C. blue phase. In this state, ultraviolet light (ultraviolet light intensity: 23 mWcm-2 (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer / liquid crystal composite material A-1 thus obtained maintained an optically isotropic liquid crystal phase even when cooled to room temperature.

  As shown in FIG. 1, the electrodes of the comb-shaped electrode substrate are alternately arranged with electrodes 1 extending in the right direction from the left connection electrode portion and electrodes 2 extending in the left direction from the right connection electrode portion. . Accordingly, when there is a potential difference between the electrode 1 and the electrode 2, on the comb-shaped electrode substrate as shown in FIG. 1, when attention is paid to one electrode, the upper direction and the lower direction on the drawing are two directions. A state in which an electric field exists can be provided.

(Example 5)
The cell sandwiched with the polymer / liquid crystal composite material A-1 obtained in Example 4 was set in the optical system shown in FIG. 2, and the electro-optical characteristics were measured. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) is used as the light source, the incident angle to the cell is perpendicular to the cell surface, and the line direction of the comb-shaped electrode is 45 with respect to the Polarizer and Analyzer polarizer, respectively. The cell was set in the optical system so that the temperature was 0 °. The relationship between applied voltage and transmittance at room temperature was examined. When a 43 V rectangular wave was applied, the transmittance was 87% and the transmitted light intensity was saturated.
Thus, even when the acrylic acid-4- (4-propylphenoxy) -butyl ester (2-1-2) synthesized in Example 3 is used, the optically isotropic polymer / liquid crystal composite material has a low voltage. It was driven by.

  Examples of the utilization method of the present invention include an optical element such as a display element using a polymer / liquid crystal composite.

1 ... Electrode 1
2 ... Electrode 2
3 ... Light source 4 ... Polarizer (Polarizer)
5 ... Comb electrode cell 6 ... Analyzer (polarizer) (Analyzer)
7 ... Photodetector

Claims (16)

An optically isotropic liquid crystal composition containing at least one chiral compound K represented by the achiral liquid crystal component A and the general formulas (K1) to (K5) is added to the general formulas (2-1) to (2- A monomer / liquid crystal mixture obtained by further mixing one or more polymerizable monomers represented by 3).

(In the formula (K1) ~ (K5), R K is independently hydrogen, halogen, -C≡N, alkyl having -N = C = O, -N = C = S or C 1-20 And any —CH ₂ — in the alkyl is replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C—. Any hydrogen in the alkyl may be replaced by a halogen; ^AK is independently an aromatic 6-8 membered ring, a non-aromatic 3-8 membered ring,
Alternatively, it is a condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced with halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — in the ring is —O—. , -S- or -NH-, and -CH = may be replaced by -N =;
Y ^K is independently hydrogen, halogen, alkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, aromatic 6 to 8 membered ring, non-aromatic 3 to 8 membered ring, or A condensed ring having 9 to 20 carbon atoms, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — may be —O—, —S— or It may be replaced by -NH-, -CH = may be replaced by -N =; ^{Z K} is independently a single bond, or an alkylene having 1 to 8 carbon atoms, arbitrary -CH ₂ -Is -O-, -S-, -COO-, -OCO-, -CSO-, -OCS-, -N = N-, -CH = N-, -N = CH-, -CH = CH-. , -CF = CF- or -C≡C-, where any hydrogen is replaced by halogen Well; ^{X K} is a single _{bond, -COO -, - OCO -,} - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, or _-CH 2 CH ₂ - and are; mK is It is an integer of 1-4. )

In formulas (2-1) to (2-3),
R ^a is linear or branched alkyl having 1 to 30 carbon atoms, or linear or branched alkyl having 2 to 30 carbon atoms;
R ^b is a linear or branched alkylene having 1 to 30 carbon atoms;
Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently hydrogen, fluorine, or a methyl group;
R ^d is hydrogen or methyl. In Formula (2-1), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is hydrogen. 2. The monomer / liquid crystal mixture according to claim 1, containing a polymerizable monomer. In Formula (2-1), R ^a is linear or branched alkyl having 1 to 30 carbon atoms, R ^b is linear alkylene having 1 to 30 carbon atoms, and R ^d is methyl. 2. The monomer / liquid crystal mixture according to claim 1, containing a polymerizable monomer. In Formula (2-2), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is hydrogen. 2. The monomer / liquid crystal mixture according to claim 1, containing a polymerizable monomer. In Formula (2-2), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is methyl. The monomer / liquid crystal mixture according to claim 1, comprising at least one polymerizable monomer. In formula (2-3), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is hydrogen. 2. The monomer / liquid crystal mixture according to claim 1, containing a polymerizable monomer. In Formula (2-3), R ^a is a linear or branched alkyl having 1 to 30 carbon atoms, R ^b is a linear alkylene having 1 to 30 carbon atoms, and R ^d is methyl. 2. The monomer / liquid crystal mixture according to claim 1, containing a polymerizable monomer. The monomer / liquid crystal mixture according to claim 1, wherein the achiral liquid crystal component A contains a compound represented by the general formula (1-A).

(In the general formula (1-A), R ¹¹ is hydrogen, alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, — OCO- or —C≡C— may be replaced, but two consecutive —CH ₂ — are not replaced by —O—, and any hydrogen in the alkyl may be replaced by halogen. Ring A ¹¹ , ring A ¹² , ring A ¹³ and ring A ¹⁴ are independently 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran; -3,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-2,6-diyl, bicyclo [2,2,2] octane-1,4-diyl, 1,4 -Cyclohexylene, or 2, , 7-Trio key is rust cyclo [2,2,2] octane-1,4-diyl, any hydrogen in these rings may be replaced by halogen; ^{Z 11,} Z ^{12, Z 13} and Z ¹⁴ is independently a single bond or alkylene having 1 to 4 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —S—, —COO—, —OCO—, —CSO—. , -OCS-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen in the alkylene may be replaced by halogen; L ¹¹ and L ¹² Are each independently hydrogen or halogen; X ¹¹ is halogen, —C≡N, —N═C═S, —C≡C—C≡N, —SF ₅ , —CHF ₂ , —CF ₃ , — _{CF 2 CH 2 F, -CF 2} CHF 2, -CF 2 _{F 3, - (CF 2)} 3 -F, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CF 2) 4 -F, - (CF 2) 5 -F, -OCHF 2, -OCF 3, _{-OCF 2 CH 2 F, -OCF 2} CHF 2, -OCH 2 CF 3, -OCF 2 CF 3, -O- (CF 2) 3 -F, -OCF 2 CHFCF 3, -OCHFCF 2 CF 3, -O _{- (CF 2) 4 -F,} -O- (CF 2) 5 -F, -CH = CF 2, -CH = CHCF 3 or _{-CH = CHCF 2 CF 3,;} l and m are independently 0 Or 1. The achiral liquid crystal component A contains at least one compound represented by any one of the following formulas (1-Aa) to (1-Aj). The monomer / liquid crystal mixture described in 1.

(In the formulas (1-Aa) to (1-Aj), R ¹¹ is alkyl having 2 to 8 carbon atoms, and X ¹¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH. ₂ F, —OCF ₃ , —OCHF ₂ , —OCH ₂ F or —C═C—CF ₃ , (F) represents hydrogen or fluorine.)   The achiral liquid crystal component A contains 50 to 100% by weight of the compound represented by the general formula (1-A), and the chiral compound K is represented by the general formulas (K1) to (K5). The monomer / liquid-crystal mixture of any one of Claims 1-9 containing 0.1-30 weight% of 1 or more types of a compound. The monomer / liquid crystal mixture according to any one of claims 1 to 10, further comprising at least one bifunctional monomer represented by the general formula (M2).

^{R C -Y M - (A M} -Z M) m1 -A M -Y M -R C (M2)

In formula (M2), R ^C each independently represents a polymerizable group of groups (M3-1) to (M3-7); A ^M is each independently aromatic or non-aromatic. A 5-membered ring, a 6-membered ring or a condensed ring having 9 to 20 carbon atoms, in which —CH ₂ — is —O—, —NH—, or —NCH ₃ —, and —CH ₂ — = May be replaced by -N =, and the hydrogen atom in the ring may be replaced by halogen and alkyl having 1 to 5 carbon atoms or alkyl halide; Y ^M is independently a single bond or carbon An alkylene having a number of 1 to 20, in which any —CH ₂ — is replaced by —O—, —S—, —CH═CH—, —C≡C—, —COO—, or —OCO—; It is well also; ^{Z M} are each independently a single _{bond, - (CH 2) m3 -} , - _{(CH 2) m3 -, -} (CH 2) m3 O -, - O (CH 2) m3 O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - (CF 2 ) ₂ −, — (CH ₂ ) ₂ —COO—, —OCO— (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH—, —C≡C—COO—, —OCO —C≡C—, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH —C≡C—, —OCF ₂ — (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CF ₂ O—, —OCF ₂ — or —CF ₂ O— (wherein m3 is 1 to 20 M1 is an integer from 1 to 6;

Here, R ^d in the group (M3-1) to the group (M3-7) is each independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen is replaced with halogen. May be. The monomer / liquid crystal mixture according to any one of claims 1 to 10, further comprising at least one bifunctional monomer represented by the general formula (M2-15).

In the formula, R ^C is an acrylate group having 1 to 30 or a methacrylate group; Y ^M is each independently a single bond or alkylene having 1 to 20 carbon atoms; Z ^M is each independently a single bond; _{- (CH 2) m3 -,} - O (CH 2) m3 -, - (CH 2) m3 O -, - O (CH 2) m3 O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - ( CF 2) 2 -, - (CH 2) 2 -COO -, - OCO- (CH 2) 2 -, - CH = CH-COO -, - OCO-CH = CH-, -C≡C-COO -, - OCO- C≡C -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - CF = CF -, - C≡C -CH = CH -, - CH = CH-C≡C -, - OCF 2 - (CH 2) 2 -, - (CH 2) 2 -CF 2 O -, - OCF ₂ — or —CF ₂ O— (wherein m ³ is an integer of 1 to 20); and 1,4-phenylene and (F) are connected by a straight line, one or two One hydrogen represents 1,4-phenylene which may be replaced by fluorine, and 1,4-phenylene and (F, Me) are connected by a straight line when one or two hydrogens are fluorine or methyl. It represents 1,4-phenylene which may be replaced.   The monomer / liquid crystal mixture according to claim 1, which exhibits a chiral nematic phase at a temperature of −20 ° C. to 70 ° C. and has a helical pitch of 700 nm or less in at least a part of this temperature range.   A polymer / liquid crystal composite material used for an element driven by an optically isotropic liquid crystal phase, obtained by polymerizing the monomer / liquid crystal mixture according to claim 1.   An optically isotropic liquid crystal phase obtained by polymerizing the monomer / liquid crystal mixture according to any one of claims 1 to 13 in a non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase. Polymer / liquid crystal composite material used for driven elements. Electric field application in which electrodes are arranged on one or both surfaces, and an electric field is applied to the liquid crystal composition or polymer / liquid crystal composite material disposed between the substrates, and the liquid crystal composition or polymer / liquid crystal composite material via the electrodes a liquid crystal device comprising a means, the polymer / liquid crystal element composite material is a polymer / liquid crystal composite material according to any one of claims 14 or 15.

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