JP7248021B2 - liquid crystal compositions, monomer/liquid crystal mixtures, polymer/liquid crystal composites, liquid crystal elements and chiral compounds - Google Patents

Description

The present invention relates to liquid crystal compositions, monomer/liquid crystal mixtures, polymer/liquid crystal composites, liquid crystal devices and chiral compounds containing chiral and achiral components.

A chiral nematic liquid crystal composition composed of a liquid crystal composition, a chiral compound, and a photopolymerizable monomer has been developed as a technology that enables low-voltage driving, which is an important characteristic required for the practical use of light-scattering liquid crystal display devices. Light modulating layers using such materials are disclosed (Patent Documents 1 to 3). A light control layer produced by photopolymerizing a photopolymerizable monomer contained in a chiral nematic liquid crystal composition in the presence of a polymerization initiator is used in a low voltage driven liquid crystal device. Specifically, it is a liquid crystal device that can electrically control the blocking and transmission of outside light and visibility. It is used for dimming windows to block or transmit light.
Similar to the isotropic phase in nematic liquid crystal materials (hereinafter sometimes referred to as “non-liquid crystal isotropic phase”), the blue phase, which is a type of optically isotropic liquid crystal phase, also has an electric birefringence value (isotropic medium Kerr effect [Δn(E)=KλE ² (K: Kerr coefficient (Ker constant), λ: wavelength)] is observed. Further, 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 disclosed (Patent Documents 4 to 9, Non-Patent Document 1. ~3). The blue phase is proposed for application not only to display devices in this mode, but also to tunable filters using electrical birefringence, wavefront control devices, liquid crystal lenses, aberration correction devices, aperture control devices, and optical head devices. (Patent Documents 7 to 9).

JP-A-5-241119 JP-A-5-281525 JP-A-5-289064 JP 2003-327966 A WO2005/90520 JP 2005-336477 A WO2005/080529 JP 2005-157109 A JP 2006-127707 A

Nature Materials, 1, 64, (2002) Adv. Mater., 17, 96, (2005) Journal of the SID, 14, 551, (2006) Soft Matter, 10, 6582, (2014)

A liquid crystal composition exhibiting a chiral nematic phase or an optically isotropic phase contains a chiral component and an achiral component. In general, the higher the helical twist power (HTP) of the chiral compound, the shorter the helical pitch of the liquid crystal can be added to the liquid crystal composition in a smaller amount of the chiral compound. Therefore, by adding a small amount of chiral compound, a liquid crystal composition having a desired helical pitch can be realized. When used in an optically isotropic liquid crystal composition, a chiral nematic phase or an optically isotropic phase is developed by adding a small amount of a chiral compound, and when used as a liquid crystal element, the driving voltage is reduced. Effects such as reduction and suppression of precipitation of chiral compounds can be expected. In the above liquid crystal composition, it is the achiral component that contributes to the characteristics of the liquid crystal element such as driving voltage and response speed, and it is possible to increase the content of the achiral component by using a chiral compound with a high HTP. It is for the sake of becoming. In addition, a chiral compound with good compatibility can consequently improve the compatibility of the liquid crystal composition, and when used as a liquid crystal element, it can be driven in a wide temperature range including low temperatures. Also, when the liquid crystal composition is prepared, the time required for dissolution can be greatly shortened, enabling efficient production and reducing the production cost.

Therefore, an object of the present invention is to provide a liquid crystal compound composed of a chiral component and an achiral component that have a large helical twist power (HTP), good compatibility with other liquid crystal compounds, and good reliability such as light resistance, and can be driven. An object of the present invention is to provide a liquid crystal composition and a liquid crystal element that require a low voltage, have high-speed response, and have good storage stability. Another object of the present invention is to provide a liquid crystal composition and a liquid crystal element which are stable against external light and have excellent light resistance and which can be used outdoors for a long period of time.

As a result of extensive research, the present inventors have solved the above problem by using a liquid crystal composition using a 9,10-ethanoanthracene-based chiral compound as a chiral component and a fluorine-based liquid crystal compound as an achiral component. I found a solution. Specifically, it is as follows.

（式（Ｋ１）において、
Ｒ^ｋ１はそれぞれ独立して、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、炭素数２～１０のアルケニルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｙ^ｋ１はそれぞれ独立して、単結合、または－（ＣＨ_２）_ｎ－であり、ｎは１～２０の整数であり；
ｎｋ１、およびｎｋ２はそれぞれ独立して、０～４の整数であり、
Ｒｏｄ^ｋ１は、部分構造式（Ｒｏｄ１）であり、
部分構造式（Ｒｏｄ１）において、
Ｒ^ｋ２は水素、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、炭素数２～１０のアルケニルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
環Ａ^ｋ１、環Ａ^ｋ２、および環Ａ^ｋ３はそれぞれ独立して、１，４－シクロヘキシレン、１，４－フェニレン、少なくとも１つの水素がフッ素で置き換えられた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、またはピリミジン－２，５－ジイルであり；
Ｚ^ｋ１、Ｚ^ｋ２、およびＺ^ｋ３はそれぞれ独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、－ＣＨ＝ＣＨ－、－ＣＦ_２ＣＦ_２－、－ＣＦ＝ＣＦ－、または－Ｃ≡Ｃ－であり；
ｍｋ１、およびｍｋ２はそれぞれ独立して、０または１の整数である。
また、下記に示す、環構造に０～４つのＲ^ｋ１が連結した部分構造（Ｘ１）および（Ｘ２）では、環構造を形成する水素のうち、０～４つの水素が、Ｒ^ｋ１で置き換えられていてもよい。）

（式（１－Ａ）および（１－Ｂ）において、
Ｒ^１１およびＲ^１２はそれぞれ独立して、水素、炭素数１～１０のアルキル、炭素数１～１０のアルコキシ、または炭素数２～１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つ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、および環Ａ^１３はそれぞれ独立して、１，４－シクロヘキシレン、１，４－フェニレン、少なくとも１つの水素がフッ素で置き換えられた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、またはピリミジン－２，５－ジイルであり；
Ｚ^１１、Ｚ^１２、およびＺ^１３はそれぞれ独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、または－Ｃ≡Ｃ－であり；
Ｘ^１１はフッ素、塩素、－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であり；
Ｌ^１１およびＬ^１２はそれぞれ独立して、水素またはフッ素であり；
Ｌ^１３およびＬ^１４はそれぞれ独立して、水素、フッ素、塩素、または－Ｃ≡Ｎであるが、Ｌ^１３およびＬ^１４がともに水素であることはなく；
Ｓ^１１は水素またはメチルであり；
ｍおよびｎはそれぞれ独立して、０または１である。）[1] An achiral compound containing at least one chiral compound represented by formula (K1) as a chiral component (K) and represented by formula (1-A) or (1-B) as an achiral component (T) A liquid crystal composition containing at least one of

(In formula (K1),
Each R ^k1 is independently fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O— provided that no two consecutive —CH ₂ — are replaced by —O—, and in these groups at least one hydrogen may be replaced by a halogen;
each Y ^k1 is independently a single bond or -(CH ₂ ) _n -, where n is an integer from 1 to 20;
nk1 and nk2 are each independently an integer of 0 to 4;
Rod ^k1 is the partial structural formula (Rod1),
In the partial structural formula (Rod1),
R ^k2 is hydrogen, fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — is replaced with —O—; but no two consecutive —CH ₂ — are replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen;
Ring A ^k1 , Ring A ^k2 and Ring A ^k3 are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ^k1 , Z ^k2 and Z ^k3 are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF ₂ CF ₂ -, -CF=CF-, or -C≡C-;
mk1 and mk2 are each independently an integer of 0 or 1;
In partial structures (X1) and (X2) in which 0 to 4 R ^k1 are linked to the ring structure shown below, 0 to 4 hydrogens among the hydrogens forming the ring structure are replaced with R ^k1 may be )

(In formulas (1-A) and (1-B),
R ¹¹ and R ¹² are each independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one - CH ₂ — may be replaced by —O—, but two consecutive —CH ₂ — may not be replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen. often;
Ring A ¹¹ , ring A ¹² and ring A ¹³ are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, or -C≡C-;
X ¹¹ is fluorine, chlorine, -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 CHFCF3} , _-CHFCF2CF3 , -( _CF2 ) _{4 -} F, -( _CF2 ) ₅ -F, _-OCHF2 , _-OCF3 , _{-OCF2CH2F , -OCF2CHF2 ,} -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 ¹¹ and L ¹² are each independently hydrogen or fluorine;
L ¹³ and L ¹⁴ are each independently hydrogen, fluorine, chlorine, or —C≡N, but not both L ¹³ and L ¹⁴ are hydrogen;
S ¹¹ is hydrogen or methyl;
m and n are each independently 0 or 1; )

（式（Ｋ１－１）において、
Ｒ^ｋ１はそれぞれ独立して、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、または炭素数２～１０のアルケニルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
ｎｋ１、およびｎｋ２はそれぞれ独立して、０～４の整数であり、
Ｒｏｄ^ｋ１は、部分構造式（Ｒｏｄ１－１）または（Ｒｏｄ１－２）であり、
部分構造式（Ｒｏｄ１－１）および（Ｒｏｄ１－２）において、
Ｒ^ｋ２は水素、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、または炭素数２～１０のアルケニルであり、このアルキルにおいて中の少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
環Ａ^ｋ１、環Ａ^ｋ２、および環Ａ^ｋ３はそれぞれ独立して、１，４－シクロヘキシレン、１，４－フェニレン、少なくとも１つの水素がフッ素で置き換えられた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、またはピリミジン－２，５－ジイルであり；
Ｚ^ｋ２およびＺ^ｋ３はそれぞれ独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、－ＣＨ＝ＣＨ－、－ＣＦ_２ＣＦ_２－、－ＣＦ＝ＣＦ－、または－Ｃ≡Ｃ－であり；
ｍｋ１、およびｍｋ２はそれぞれ独立して、０または１の整数である。
また、下記に示す、環構造にＲ^ｋ１が連結した部分構造（Ｘ１）および（Ｘ２）では、環構造を形成する水素のうち、０～４つの水素が、Ｒ^ｋ１で置き換えられていてもよい。）

[2] The liquid crystal composition according to [1], wherein the chiral compound represented by formula (K1) is a chiral compound represented by formula (K1-1).

(In formula (K1-1),
Each R ^k1 is independently fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, wherein at least one —CH ₂ — is —O may be replaced by -, but no two consecutive -CH ₂ - are replaced by -O-, and in these groups at least one hydrogen may be replaced by halogen;
nk1 and nk2 are each independently an integer of 0 to 4;
Rod ^k1 is a partial structural formula (Rod1-1) or (Rod1-2),
In the partial structural formulas (Rod1-1) and (Rod1-2),
R ^k2 is hydrogen, fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — is —O—; optionally substituted, but no two consecutive —CH ₂ — are replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen;
Ring A ^k1 , Ring A ^k2 and Ring A ^k3 are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ^k2 and Z ^k3 are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ - , -CH=CH-, -CF ₂ CF ₂ -, -CF=CF-, or -C≡C-;
mk1 and mk2 are each independently an integer of 0 or 1;
In partial structures (X1) and (X2) in which R ^k1 is linked to a ring structure shown below, 0 to 4 hydrogens among the hydrogens forming the ring structure may be replaced with R ^k1 . . )

（部分構造式（Ｒｏｄ１－１Ａ）～（Ｒｏｄ１－１Ｈ）及び（Ｒｏｄ１－２Ａ）～（Ｒｏｄ１－２Ｈ）において、
Ｒ^ｋ２は水素、炭素数１～１０のアルキル、または炭素数２～１０のアルケニルであり、このアルキルにおいて中の少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
また、下記に示す１，４－フェニレンに（Ｆ）が連結した部分構造（Ｘ３）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－フェニレンを示す。）

[3] In formula (K1-1),
Each R ^k1 is independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with —O—, no two consecutive —CH ₂ — are replaced by —O— and in these groups at least one hydrogen may be replaced by halogen;
nk1 and nk2 are each independently an integer of 0 to 4;
The liquid crystal composition according to [2], wherein Rod ^k1 is any one of partial structural formulas (Rod1-1A) to (Rod1-1H) and (Rod1-2A) to (Rod1-2H) shown below.

(In the partial structural formulas (Rod1-1A) ~ (Rod1-1H) and (Rod1-2A) ~ (Rod1-2H),
R ^k2 is hydrogen, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with —O—; consecutive —CH ₂ — are not replaced by —O— and in these groups at least one hydrogen may be replaced by halogen;
Further, the partial structure (X3) in which (F) is linked to 1,4-phenylene shown below represents 1,4-phenylene in which one or two hydrogen atoms may be replaced with fluorine. )

式（１－Ａ－０１）～式（１－Ａ－２２）において、
Ｒ^１１は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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；
環Ａ^１１および環Ａ^１２は独立して、１，４－シクロヘキシレン、またはテトラヒドロピラン－２，５－ジイル、またはピリミジン－２，５－ジイルであり；
Ｘ^１１は独立して、フッ素、塩素、－ＣＦ_３、または－ＯＣＦ_３であり；
（Ｆ）は、水素またはフッ素である。[4] wherein the achiral compound represented by formula (1-A) is any one of formulas (1-A-01) to (1-A-22), [1] to [ 3] The liquid crystal composition according to any one of the above.

In formulas (1-A-01) to (1-A-22),
R ¹¹ is independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced with —O—, without two consecutive —CH ₂ — being replaced by —O—;
Ring A ¹¹ and Ring A ¹² are independently 1,4-cyclohexylene, or tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
X ¹¹ is independently fluorine, chlorine, —CF ₃ , or —OCF ₃ ;
(F) is hydrogen or fluorine.

式（１－Ｂ－０１）～式（１－Ｂ－２２）において、
Ｒ^１１およびＲ^１２は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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；
環Ａ^１１および環Ａ^１２は独立して、１，４－シクロヘキシレン、またはテトラヒドロピラン－２，５－ジイル、またはピリミジン－２，５－ジイルであり；
（Ｆ）は、水素またはフッ素である。[5] wherein the achiral compound represented by formula (1-B) is any one of formulas (1-B-01) to (1-B-22), [1] to [ 3] The liquid crystal composition according to any one of the above.

In formulas (1-B-01) to (1-B-22),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced with —O—. good, but without replacing two consecutive —CH ₂ — with —O—;
Ring A ¹¹ and Ring A ¹² are independently 1,4-cyclohexylene, or tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
(F) is hydrogen or fluorine.

[6] The liquid crystal composition according to any one of [1] to [5], wherein the content of the chiral component (K) in the liquid crystal composition is 0.1 to 30% by weight.

[7] Any one of [1] to [6], wherein the content of the compound represented by formula (1-A) or (1-B) in the achiral component (T) is 50 to 100% by weight The described liquid crystal composition.

[8] [1] to [6], wherein the content of the compound represented by formula (1-A) in the achiral component (T) is 50 to 100% by weight and exhibits an optically isotropic liquid crystal phase; ] The liquid crystal composition according to any one of the above.

（式（Ｋ２）～（Ｋ８）中、Ｒ^Ｋはそれぞれ独立して、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、このアルキル中の少なくとも１つの－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、このアルキル中の少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ａ^Ｋはそれぞれ独立して、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、これらの環中の少なくとも１つの水素はハロゲン、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はそれぞれ独立して、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、これらの環の少なくとも１つの水素がハロゲン、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はそれぞれ独立して単結合、または炭素数１～８のアルキレンであるが、少なくとも１つの－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、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｘ^Ｋはそれぞれ独立して、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、または－ＣＨ_２ＣＨ_２－であり；
ｍＫはそれぞれ独立して、１～４の整数である。）[9] The liquid crystal composition according to any one of [1] to [8], which further contains at least one chiral compound represented by formulas (K2) to (K8) in addition to the chiral component (K).

(In formulas (K2) to (K8), R ^K is each independently hydrogen, halogen, —C≡N, —N═C═O, —N═C═S, or alkyl having 1 to 20 carbon atoms. and at least one —CH ₂ — in the alkyl is replaced with —O—, —S—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— at least one hydrogen in the alkyl may be replaced with a halogen;
Each A ^K is independently an aromatic 6- to 8-membered ring, a non-aromatic 3- to 8-membered ring, or a condensed ring having 9 to 20 carbon atoms, and at least one hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, -CH ₂ - in the ring may be replaced by -O-, -S- or -NH-, and -CH= is -N = may be replaced;
Y ^K each independently represents 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 , is a condensed ring having 9 to 20 carbon atoms, at least one hydrogen of these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — is —O—, —S optionally replaced by - or -NH- and -CH= optionally replaced by -N=;
Each Z ^K is independently a single bond or an alkylene having 1 to 8 carbon atoms, and at least one —CH ₂ — is —O—, —S—, —COO—, —OCO—, —CSO— , -OCS-, -N=N-, -CH=N-, -N=CH-, -CH=CH-, -CF=CF- or -C≡C-, and at least one hydrogen may be replaced by halogen;
each X ^K is independently a single bond, -COO-, -OCO- _, -CH ₂ O-, -OCH 2 -, -CF ₂ O-, -OCF ₂ -, or -CH ₂ CH ₂ -; ;
Each mK is independently an integer of 1-4. )

[10] A monomer/liquid crystal mixture containing the liquid crystal composition according to any one of [1] to [9] and a polymerizable monomer.

[11] The monomer/liquid crystal according to [10], which exhibits a chiral nematic phase in a temperature range of at least 1°C at -20°C to 70°C, and has a helical pitch of 700 nm or less in at least part of this temperature range. blend.

[12] The monomer/liquid crystal mixture of [10], wherein the liquid crystal composition has an optically isotropic liquid crystal phase.

[13] The monomer/liquid crystal mixture according to any one of [10] to [12], wherein the content of the polymerizable monomer is in the range of 0.1 to 50% by weight with respect to the total amount of the monomer/liquid crystal mixture.

[14] A liquid crystal device driven by an optically isotropic liquid crystal phase obtained by polymerizing the monomer/liquid crystal mixture according to [10] in a non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase A polymer/liquid crystal composite material used for

[15] A polymer/liquid crystal composite material obtained by polymerizing the monomer/liquid crystal mixture described in [10] and used for a light-scattering liquid crystal device driven by a chiral nematic phase.

[16] Provided with a pair of substrates having electrodes, a light control layer sandwiched between the pair of substrates, and an electric field applying means for applying an electric field to the light control layer via the electrodes. A liquid crystal element,
A liquid crystal device, wherein at least one of the pair of substrates is transparent, and the light control layer is composed of the polymer/liquid crystal composite material according to [14] or [15].

[17] The liquid crystal device according to [16], wherein the polymer/liquid crystal composite material exhibits a chiral nematic phase and constitutes a light scattering liquid crystal device.

[18] The liquid crystal device according to [16] or [17], wherein the content of the polymer in the polymer/liquid crystal composite material is in the range of 0.1 to 50% by weight.

[19] A chiral compound represented by the following formula (K101), (K102), or (K103).

As used herein, the term "liquid crystal compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds having no liquid crystal phase but useful as components of liquid crystal compositions. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element are sometimes abbreviated as a compound, a composition, and an element, respectively.

In this specification, "liquid crystal element" is a general term for liquid crystal display panels and liquid crystal display modules. The upper temperature limit of the nematic phase is the nematic-to-isotropic phase transition temperature and is sometimes abbreviated simply as the clearing point or upper temperature limit. The lower limit temperature of the nematic phase is sometimes simply abbreviated as the lower limit temperature.

In this specification, the compound represented by formula (1) may be abbreviated as compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like. In the chemical formulas, symbols such as A ¹¹ and A ¹² surrounded by hexagons correspond to ring structures A ¹¹ and A ¹² , respectively.
These are sometimes abbreviated as "Ring A ¹¹ " and "Ring A ¹² ". "Ring structure" refers to a cyclic group, including benzene ring, naphthalene ring, cyclohexene ring, bicyclooctane ring, cyclohexane ring and the like. Here, a ring structure containing 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 counted as one ring structure.
A plurality of the same symbols such as rings A ^k1 and Y ^k1 are described in the same formula or different formulas, but these may be the same or different.
A wavy line in a chemical formula indicates a bonding site.

"At least one" indicates that there is no limitation in number as well as position, but does not include zero number. The expression that at least one A may be replaced by B, C or D means if at least one A is replaced by B, if at least one A is replaced by C and if at least one A is replaced by D In addition to the case where multiple A's are replaced by at least two of BD's.
For example, alkyl in which at least one -CH ₂ - may be replaced with -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 form —O—O—. It is also not preferred that the terminal —CH ₂ — in alkyl is replaced with —O—.
Also, in this specification, "%" means "% by weight" unless otherwise specified.

A liquid crystal composition containing a chiral component and an achiral component according to an embodiment of the present invention has good light resistance, and is thus suitably used for a liquid crystal element. Since the chiral compound according to the embodiment of the present invention has a large HTP and high compatibility with the achiral component, it is possible to adjust the pitch to 0.5 μm or less. In addition, it can exhibit a liquid crystal phase over a wide temperature range including low temperatures.
Furthermore, since a more effective light scattering property can be obtained, a liquid crystal element using this liquid crystal composition can be driven at a low voltage, and exhibits a high contrast due to a large change in light scattering between when a voltage is applied and when no voltage is applied. It can be applied to liquid crystal devices.
In order to bring out the performance of the liquid crystal composition according to the embodiment of the present invention, it is preferable to use a chiral nematic liquid crystal or a cholesteric liquid crystal together. In addition to the chiral compound represented by the formula (K1), the liquid crystal composition according to the embodiment of the present invention includes a material generally recognized as a liquid crystal material in this technical field, and a chiral compound represented by the formula (K1). A chiral compound or the like other than the compound may be added as appropriate.

Also, an optically isotropic liquid crystal composition can be efficiently prepared in a short time. A liquid crystal composition, a liquid crystal composition exhibiting an optically isotropic liquid crystal phase, and a polymer/liquid crystal composite material according to an embodiment of the present invention exhibit a relatively large Kerr coefficient. That is, it exhibits a relatively low drive voltage. The optically isotropic liquid crystal composition and the polymer/liquid crystal composite material according to the embodiment of the present invention have a high response speed.
Liquid crystal compositions and polymer/liquid crystal composite materials exhibiting an optically isotropic liquid crystal phase according to embodiments of the present invention can be used over a wide temperature range. Based on these effects, the liquid crystal composition and polymer/liquid crystal composite material exhibiting an optically isotropic liquid crystal phase according to the embodiments of the present invention are suitable for liquid crystal elements such as liquid crystal display elements for high-speed response. can be used for

1 shows a comb-shaped electrode substrate used in Examples. The optical system used in the example is shown. It is a figure which shows the cross section of an example of the structure of a liquid crystal element. FIG. 4 is a diagram showing a cross section of another example of the structure of the liquid crystal element;

1. Liquid Crystal Composition of the Present Invention A first aspect of the present invention is a liquid crystal composition that can be used in a liquid crystal device driven in a chiral nematic phase or an optically isotropic phase.
A liquid crystal composition according to an embodiment of the present invention has a compound represented by formula (K1) as a chiral component and an achiral component. Here, the handedness of the chiral component does not matter. A liquid crystal composition according to an embodiment of the present invention preferably exhibits a chiral nematic phase or an optically isotropic phase.
Compounds contained in the liquid crystal composition according to the embodiment of the present invention are generally synthesized by a known method such as a method of reacting necessary components at high temperature.
Further, each element of the compound constituting the liquid crystal composition according to the embodiment of the present invention can be used as an analogue composed of an isotope element as long as there is no significant difference in physical properties.
In the liquid crystal composition according to the embodiment of the present invention, the content of the chiral component (K) is usually 0.1 to 30% by weight, preferably 0.1 to 10% by weight.

1.1 Chiral Nematic Phase Liquid crystal compositions according to embodiments of the present invention include those having a chiral nematic phase. A chiral nematic phase can be obtained by adding a small amount of a chiral compound to an achiral component composed of a compound that develops a nematic phase. The helical pitch (hereinafter sometimes simply referred to as "pitch") of the liquid crystal composition used in the embodiments of the present invention is 0.3 to obtain a sufficient contrast between opacity and transparency due to light scattering. It is preferably ˜5 μm. Generally, when the helical pitch is in the range of 0.3 to 0.5 μm, the transparency due to light scattering is relatively high, and when the helical pitch is in the range of 0.6 to 5 μm, the opacity due to light scattering is relatively high.
For use as a light modulating material, the compound (K1) has a large HTP and is highly compatible with the compound (1-A) or (1-B), so pitch adjustment of 0.5 μm or less is possible. Furthermore, since effective light scattering properties are obtained and the stability to light is high, it is possible to provide a liquid crystal device which can obtain high contrast when driven at a low voltage and which has high light resistance.

1.2 Optically isotropic liquid crystal phase Liquid crystal compositions according to embodiments of the present invention include those having an optically isotropic liquid crystal phase. Here, when the liquid crystal composition has optical isotropy, it means that the liquid crystal molecules are arranged macroscopically and therefore optically isotropic, but the liquid crystal order exists microscopically. It means to
In the present specification, the term "optically isotropic liquid crystal phase" refers to a phase exhibiting an optically isotropic liquid crystal phase instead of fluctuations. ) is an example.
Blue phases are generally classified into three types (blue phase I, blue phase II, and blue phase III), and all three blue phases are optically active and isotropic. In blue phases such as blue phase I and blue phase II, two or more types of diffracted light due to Bragg reflection from different lattice planes are observed.
In order to develop an optically isotropic liquid crystal phase in the liquid crystal composition according to the embodiment of the present invention, the helical pitch based on the microscopic liquid crystal order is preferably 1000 nm or less.
Since the electric birefringence in the optically isotropic liquid crystal phase increases as the pitch increases, the type and content of the chiral component can be adjusted as long as the desired optical properties (transmittance, diffraction wavelength, etc.) are satisfied. Electric birefringence can be increased by setting a long pitch.
Further, in the present specification, the “non-liquid crystal isotropic phase” is an isotropic phase generally defined, that is, a disordered phase, and even if a region with a non-zero local order parameter is generated, is an isotropic phase due to fluctuations. For example, an isotropic phase that appears 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 also to the chiral liquid crystal compound in this specification.

式（Ｋ１）において、
Ｒ^ｋ１はそれぞれ独立して、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、または炭素数２～１０のアルケニルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよい。
好ましい例としては、水素、フッ素、炭素数１～５のアルキル、炭素数２～５のアルケニル、および炭素数１～５のアルコキシである。
Ｙ^ｋ１はそれぞれ独立して、単結合、または－（ＣＨ_２）_ｎ－であり、ｎは１～２０の整数である。
好ましい例としては、単結合、－ＣＨ_２ＣＨ_２－、－（ＣＨ_２）_４－、または－（ＣＨ_２）_６－、であり、ｎが小さいとＨＴＰが大きくなり、ｎが大きいと相溶性が良くなる傾向がある。
ｎｋ１、およびｎｋ２はそれぞれ独立して、０～４の整数である。
好ましい例としては、０、１、または２であり、ｎｋ１が１または２のときは液晶組成物での相溶性が良くなる傾向がある。
Ｒｏｄ^ｋ１は、部分構造式（Ｒｏｄ１）であり、
部分構造式（Ｒｏｄ１）において、
Ｒ^ｋ２は水素、フッ素、塩素、－Ｃ≡Ｎ、炭素数１～１０のアルキル、または炭素数２～１０のアルケニルであり、このアルキルにおいて中の少なくとも１つの－ＣＨ_２－は－Ｏ－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、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよい。
好ましい例としては、炭素数１～６のアルキル、炭素数２～７のアルケニル、または炭素数１～７のアルコキシである。1.3 Chiral Component (K)
1.3.1 Properties of Chiral Compound (K1) As a chiral component (K) contained in the liquid crystal composition according to the embodiment of the present invention, a compound represented by the following formula (K1) can be mentioned.

In formula (K1),
Each R ^k1 is independently fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, wherein at least one —CH ₂ — is —O may be replaced by -, but two consecutive -CH ₂ - are not replaced by -O-, and in these groups at least one hydrogen may be replaced by halogen.
Preferred examples are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, alkenyl having 2 to 5 carbon atoms, and alkoxy having 1 to 5 carbon atoms.
Each Y ^k1 is independently a single bond or -(CH ₂ ) _n -, where n is an integer of 1-20.
Preferred examples are a single bond, —CH ₂ CH ₂ —, —(CH ₂ ) ₄ —, or —(CH ₂ ) ₆ —. tends to get better.
nk1 and nk2 are each independently an integer of 0-4.
Preferable examples are 0, 1, or 2, and when nk1 is 1 or 2, the compatibility in the liquid crystal composition tends to be improved.
Rod ^k1 is the partial structural formula (Rod1),
In the partial structural formula (Rod1),
R ^k2 is hydrogen, fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — is —O—; They may be substituted, but no two consecutive —CH ₂ — are replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen.
Preferred examples are alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 7 carbon atoms, or alkoxy having 1 to 7 carbon atoms.

A preferred example of the partial structural formula is (Rod1-1) or (Rod1-2). HTP is high when (Rod1-1), and the liquid crystal composition is relatively high when (Rod1-2). have good compatibility.
Ring A ^k1 , Ring A ^k2 and Ring A ^k3 are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl.
Preferred examples are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which one or two hydrogen atoms are replaced with fluorine, or 1,3-dioxane-2,5-diyl. , the HTP of the compound is large, and the compatibility with other liquid crystal compositions is good.

Z ^k1 , Z ^k2 and Z ^k3 are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF ₂ CF ₂ -, -CF=CF-, or -C≡C-;
Preferred examples are a single bond, -COO-, -OCO-, alkylene having 1 to 10 carbon atoms, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, or -OCF ₂ -. In the case of these substituents, both HTP and compatibility in the liquid crystal composition are well balanced.
mk1 and mk2 are each independently an integer of 0 or 1;
A compound in which mk1+mk2 is 1 has good compatibility in a liquid crystal composition. Compounds with mk1+mk2=2 tend to have high HTP.

When there are multiple identical symbols such as R ^k1 , R ^k2 , A ^k1 , Z ^k1 , nk1, or nk2, they may be the same or different.
The alkyl having 1 to 10 carbon atoms is more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl, and the like.

A preferred example of the chiral compound represented by formula (K1) is a compound represented by formula (K1-1), wherein Rod ^k1 is (Rod1-1), and among formula (K1-1) , Rod ^k1 represented by (Rod1-1C), (Rod1-1D), (Rod1-1F) and (Rod1-1G) are more preferred. All of them have high HTP and relatively good compatibility with liquid crystal compositions.

In general, the content of the chiral component in the liquid crystal composition according to the embodiment of the invention is preferably 0.1 to 20% by weight, particularly preferably 1 to 10% by weight. A liquid crystal composition containing a chiral component within these ranges tends to have an optically isotropic liquid crystal phase.
A polymer/liquid crystal composite material, which will be described later, can be obtained using the liquid crystal composition according to the embodiment of the present invention. When the polymer/liquid crystal composite is used as a light modulating material, the helical pitch in the liquid crystal composition should be between 0.3 and 0.3 to obtain sufficient contrast between opacity and transparency due to light scattering. 0.5 μm, particularly preferably in the range from 0.6 to 5 μm.
Moreover, when the liquid crystal composition according to the embodiment of the present invention is used in a liquid crystal display device, it is preferable that the concentration of the chiral component is adjusted so that substantially no diffraction or reflection is observed in the visible region.
The chiral compound constituting the chiral component contained in the liquid crystal composition according to the embodiment of the present invention may be one kind or two or more kinds.
When two or more chiral compounds are used, it is preferable to use chiral compounds having the same twist direction so as not to offset HTP. For the purpose of adjusting the temperature dependence of the helical pitch, a combination of chiral compounds with opposite twist directions can be used.

1.3.2 Synthesis of Chiral Compound (K1) Next, synthesis of the compound represented by Formula (K1) will be described. Compound (K1) can be synthesized by appropriately combining techniques in synthetic organic chemistry. Methods for introducing desired terminal groups, rings and linking groups to starting materials include Organic Synthesis (John Wiley & Sons, Inc), Organic reactions (John Wiley & Sons, Inc), Comprehensive・It is described in Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc.
There are a plurality of methods for synthesizing the compound (K1), and it is possible to appropriately synthesize the compound (K1) with reference to the examples and publications of the present specification.
First, an example of a method for producing a common intermediate, compound (15), will be described using a scheme.

(1) Preparation and synthesis of anthracene derivative (15)

Anthracene derivatives can be synthesized from commercially available compounds by general organic synthesis methods. Commercially available compounds include, for example, compounds (ref.001) and (ref.002).
When R ^k1 is alkyl, alkenyl, alkynyl, or alkoxy, for example, compound (102) is obtained by subjecting compound (101) to a coupling reaction with an appropriate lithium reagent or an alkyl halide in the presence of a metal catalyst. be able to. Similarly, by reacting compound (101) with a fluorinating agent such as N-benzenesulfonimide when R ^k1 is fluorine and a cyanide such as copper cyanide when R ^k1 is —CN, respectively, A compound (103) and a compound (104) can be obtained.

(2) Synthesis of compounds (K1-1) and (K1-2)

Fumaryl chloride (111) is commercially available. Optically active ethyl lactate (112) is commercially available in either (S) form or (R) form. Compound (113) can be obtained by reacting fumaryl chloride (111) with a base such as triethylamine on optically active ethyl lactate (112).
Thereafter, compound (113) and anthracene derivative (114) are stereoselectively converted to compound (114) by a Diels-Alder reaction, which can then be derived into compound (115) by reacting an excess amount of a base.
Compound (K1-1) according to an embodiment of the present invention can be obtained by adding dicyclohexylcarbodiimide (DCC) and dimethylaminopyridine (DMAP) to compound (115) and reacting with a suitable phenol derivative (Rod ^k1 —OH). . Furthermore, compound (K1-2) can be obtained by reacting compound (K1-1) with a reducing agent such as LAH.

Next, an example of a method for producing the bonding group Z ^k1 will be explained using a scheme. In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. Multiple MSG ¹ (or MSG ² ) used in the schemes may be the same or different. Compounds (1A) to (1K) correspond to compound (K1).

アリールホウ酸（２１）と公知の方法で合成される化合物（２２）とを、炭酸塩水溶液とテトラキス（トリフェニルホスフィン）パラジウムのような触媒の存在下で反応させて化合物（１Ａ）を合成する。この化合物（１Ａ）は、公知の方法で合成される化合物（２３）にｎ－ブチルリチウムを、次いで塩化亜鉛を反応させ、ジクロロビス（トリフェニルホスフィン）パラジウムのような触媒の存在下で化合物（２２）を反応させることによっても合成される。(I) Formation of single bond

Aryl boric acid (21) and compound (22) synthesized by a known method are reacted in the presence of an aqueous carbonate solution and a catalyst such as tetrakis(triphenylphosphine)palladium to synthesize compound (1A). This compound (1A) is prepared by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride to obtain compound (22) in the presence of a catalyst such as dichlorobis(triphenylphosphine)palladium. ) can also be synthesized by reacting

化合物（１Ｂ）をローソン試薬のような硫黄化剤で処理して化合物（２６）を得る。化合物（２６）をフッ化水素ピリジン錯体とＮＢＳ（Ｎ－ブロモスクシンイミド）でフッ素化し、－ＣＦ_２Ｏ－を有する化合物（１Ｃ）を合成する（M. Kuroboshi et al., Chem. Lett., 1992，827.を参照）。化合物（１Ｃ）は化合物（２６）を（ジエチルアミノ）サルファートリフルオリド（ＤＡＳＴ）でフッ素化しても合成される（W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768.を参照）。この方法によって－ＯＣＦ_２－を有する化合物も合成できる。Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.に記載の方法によってこれらの結合基を生成させることも可能である。(II) Generation of —CF ₂ O— and —OCF ₂ —

Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to give compound (26). Compound (26) is fluorinated with hydrogen fluoride-pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having —CF ₂ O— (M. Kuroboshi et al., Chem. Lett., 1992). , 827.). Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino)sulfur trifluoride (DAST) (see WH Bunnelle et al., J. Org. Chem. 1990, 55, 768.). Compounds having —OCF ₂ — can also be synthesized by this method. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480. It is also possible to generate these linking groups.

化合物（２２）をｎ－ブチルリチウムで処理した後、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）などのホルムアミドと反応させてアルデヒド（２８）を得る。公知の方法で合成されるホスホニウム塩（２７）をカリウムｔ－ブトキシドのような塩基で処理して発生させたリンイリドを、アルデヒド（２８）に反応させて化合物（１Ｄ）を合成する。反応条件によってはシス体が生成するので、必要に応じて公知の方法によりシス体をトランス体に異性化する。(III) Formation of -CH=CH-

Compound (22) is treated with n-butyllithium and then reacted with a formamide such as N,N-dimethylformamide (DMF) to give aldehyde (28). A phosphorus ylide generated by treating a phosphonium salt (27) synthesized by a known method with a base such as potassium t-butoxide is reacted with an aldehyde (28) to synthesize a compound (1D). Depending on the reaction conditions, the cis isomer is produced, so the cis isomer is isomerized to the trans isomer by a known method, if necessary.

化合物（１Ｄ）をパラジウム炭素のような触媒の存在下で水素化することにより、化合物（１Ｅ）を合成する。Generation of (IV)-(CH ₂ ) ₂ -

Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium on carbon.

ホスホニウム塩（２７）の代わりにホスホニウム塩（２９）を用い、項（ＩＩＩ）または項（ＩＶ）の方法に従って－（ＣＨ_２）_２－および－ＣＨ＝ＣＨ－を有する化合物を得る。これを接触水素化して化合物（１Ｆ）を合成する。Generation of (V)-(CH ₂ ) ₄ -

Substituting the phosphonium salt (29) for the phosphonium salt (27), the compound having --(CH ₂ ) ₂ -- and --CH=CH- is obtained according to the method of section (III) or section (IV). This is catalytically hydrogenated to synthesize compound (1F).

ジクロロパラジウムとハロゲン化銅との触媒存在下で、化合物（２３）に２－メチル－３－ブチン－２－オールを反応させたのち、塩基性条件下で脱保護して化合物（３０）を得る。ジクロロパラジウムとハロゲン化銅との触媒存在下、化合物（３０）を化合物（２２）と反応させて、化合物（１Ｇ）を合成する。(VI) Generation of -C≡C-

Compound (23) is reacted with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, and then deprotected under basic conditions to obtain compound (30). . Compound (1G) is synthesized by reacting compound (30) with compound (22) in the presence of a catalyst of dichloropalladium and copper halide.

化合物（２２）をｎ－ブチルリチウムで処理したあと、テトラフルオロエチレンを反応させて化合物（３１）を得る。化合物（２２）をｎ－ブチルリチウムで処理した後、化合物（３１）と反応させて化合物（１Ｈ）を合成する。(VII) Generation of -CF=CF-

Compound (22) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (31). Compound (22) is treated with n-butyllithium and then reacted with compound (31) to synthesize compound (1H).

化合物（２８）を水素化ホウ素ナトリウムなどの還元剤で還元して化合物（３２）を得る。これを臭化水素酸などでハロゲン化して化合物（３３）を得る。炭酸カリウムなどの存在下で、化合物（３３）を化合物（２５）と反応させて化合物（１Ｊ）を合成する。(VIII) Formation of —CH ₂ O— or —OCH ₂ —

Compound (28) is reduced with a reducing agent such as sodium borohydride to give compound (32). This is halogenated with hydrobromic acid or the like to obtain compound (33). Compound (1J) is synthesized by reacting compound (33) with compound (25) in the presence of potassium carbonate or the like.

化合物（３２）の代わりに化合物（３４）を用いて、項（ＶＩＩＩ）の方法に従って化合物（１Ｋ）を合成する。Formation of (IX)-(CH ₂ ) ₃ O- or -O(CH ₂ ) ₃ -

Using compound (34) instead of compound (32), compound (1K) is synthesized according to the method of section (VIII).

Generation of (X)-(CF ₂ ) ₂ -
J. Am. Chem. Soc., 2001, 123, 5414. A diketone (--COCO--) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to give -(CF ₂ ) A compound with _2- is obtained.

In the liquid crystal composition according to the embodiment of the present invention, at least one of the compounds represented by the above (K2) to (K8) is added as the chiral component (K) in addition to the above chiral compound (K1). may contain.

1.4 Achiral Component The achiral component constituting the liquid crystal composition according to the embodiment of the present invention is composed of at least one achiral compound and exhibits a liquid crystal phase. An achiral component containing at least one achiral compound represented by formula (1-A) or (1-B) is suitable as a liquid crystal component used as a liquid crystal element. The liquid crystal composition according to the embodiment of the present invention includes, as the chiral component (K), a chiral compound represented by formula (K1) and an achiral compound represented by formula (1-A) or (1-B). Among the compounds, in addition to at least one achiral compound, a material generally recognized as a liquid crystal material in this technical field may be added and used as another liquid crystal material.
In addition, in the liquid crystal composition according to the embodiment of the present invention, the content of the achiral component (T) is usually 80 to 99.9% by weight, preferably 90 to 99.9% by weight.
In the liquid crystal composition according to the embodiment of the present invention, the content of the compound represented by formula (1-A) or (1-B) in the achiral component (T) is usually 50 to 100% by weight, It is preferably 90 to 100% by weight.
Furthermore, in the liquid crystal composition according to the embodiment of the present invention, the content of the compound represented by the formula (1-A) in the achiral component (T) is 50 to 100% by weight, and in that case, optically It can exhibit an anisotropic liquid crystal phase.

1.4.1 Structure of Compound Represented by Formula (1-A) or (1-B)

In the above formulas (1-A) and (1-B),
R ¹¹ and R ¹² are each independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one - CH ₂ — may be replaced by —O—, but two consecutive —CH ₂ — may not be replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen. good.
In such R ¹¹ and R ¹² , alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms is preferable. It is more preferably alkyl having 2 to 8 carbon atoms or alkenyl having 2 to 8 carbon atoms. The preferred configuration of -CH=CH- in alkenyl depends on the position of the double bond. -CH _{= CHCH3 ,} -CH= _{CHC2H5 , -CH = CHC3H7 ,} -CH _{= CHC4H9} , -C2H4CH= _CHCH3 , and -C2H4CH= _CHC2 The trans configuration is preferred in alkenyls with double bonds in odd positions such as _H5 . The cis configuration is preferred in alkenyls with double bonds in even positions such as -CH ₂ CH=CHCH ₃ , -CH ₂ CH=CHC ₂ H ₅ and -CH ₂ CH=CHC ₃ H ₇ . An alkenyl compound having a preferred configuration has a high upper temperature limit or a wide temperature range of a liquid crystal phase. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327.
Ring A ¹¹ , ring A ¹² and ring A ¹³ are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl.
Ring A ¹¹ , Ring A ¹² and Ring A ¹³ are each independently optionally substituted with halogen 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5 -diyl, or 1,4-cyclohexylene.
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, or -C≡C-.
Z ¹¹ , Z ¹² and Z ¹³ are a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O— or —OCH ₂ — are preferred, and among these, a single bond, —COO— or —CF ₂ O— is particularly preferred.
Also, in these bonds, double bonds such as -CH=CH-, -CF=CF-, -CH=CH-(CH ₂ ) ₂ -, and -(CH ₂ ) ₂ -CH=CH-, etc. For linking groups having , the configuration is preferably trans rather than cis.

X ¹¹ is fluorine, chlorine, -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 CHFCF3} , _-CHFCF2CF3 , -( _CF2 ) _{4 -} F, -( _CF2 ) ₅ -F, _-OCHF2 , _-OCF3 , _{-OCF2CH2F , -OCF2CHF2 ,} -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 .
Examples of preferred X ¹¹ are fluorine, chlorine, -C≡N, -N=C=S, -CF ₃ , -CHF ₂ , -OCF ₃ and -OCHF ₂ . Examples of the most preferred X ¹ are fluorine, chlorine, -C≡N, -N=C=S, _-CF3, and _-OCF3 .
L ¹¹ and L ¹² are each independently hydrogen or fluorine, L ¹³ and L ¹⁴ are each independently hydrogen, fluorine, chlorine, or —C≡N, but both L ¹³ and L ¹⁴ are hydrogen Never.
Among these, any one of L ¹¹ and L ¹² is preferably fluorine, and L ¹³ and L ¹⁴ are each independently preferably hydrogen, fluorine or —C≡N.
S ¹¹ is hydrogen or methyl.
m and n are each independently 0 or 1;

As the compound represented by the above formula (1-A), any one of the compounds represented by the following formulas (1-A-01) to (1-A-22) is particularly preferred.

As the compound represented by the above formula (1-B), any one of the compounds represented by the following formulas (1-B-01) to (1-B-22) is particularly preferred.

(In formulas (1-A-01) to (1-A-22) and formulas (1-B-01) to (1-B-22), R ¹¹ and R ¹² are hydrogen and have 1 to 8 carbon atoms. , alkenyl having 2 to 8 carbon atoms, or alkoxy having 1 to 8 carbon atoms, and A ¹¹ and A ¹² are 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or tetrahydropyran -2,5-diyl and X ¹¹ is fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCH ₂ F, -CN, or -C=C _—CF3 and (F) is hydrogen or fluorine.)

1.3.2 Properties of Achiral Compounds Represented by Formulas (1-A) and (1-B) The compound (1-A) has a positive dielectric anisotropy. On the other hand, compound (1-B) is a compound having negative dielectric anisotropy.
Left terminal group R ¹¹ , right terminal groups X ¹¹ and R ¹² , types of rings A ¹¹ to A 13, bonding groups Z ¹¹ to ^{Z 13 ,} terminal phenylene ring in compounds (1-A) and (1-B) and their substitution positions (L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and S ¹¹ ), bonding groups Z ¹¹ to Z ¹³ , combinations of m and n, etc., the achiral component (T ), physical properties such as clearing point, refractive index anisotropy, and dielectric anisotropy can be adjusted.
Left terminal group R ¹¹ , right terminal groups X ¹¹ and R ¹² , rings A ¹¹ to A ¹³ , bonding groups Z ¹¹ to Z ¹³ , L ¹¹ to L ¹⁴ , types of combinations of m and n, etc., and compound (1- The general relationship between A) and (1-B) physical properties is described below.

When R ¹¹ or R ¹² is a straight chain, the compounds (1-A) and (1-B) have a wide liquid crystal phase temperature range and a low viscosity. On the other hand, when R ¹¹ or R ¹² is a branched chain, the compounds (1-A) and (1-B) have good compatibility in the liquid crystal composition.
When R ¹¹ or R ¹² is alkenyl, the viscosity is low and the compatibility in the liquid crystal composition is good.
When R ¹¹ or R ¹² is alkoxy, dielectric anisotropy is increased and compatibility with the liquid crystal composition is good.

The more aromatic rings contained in rings A ¹¹ to A ¹³ , the greater the refractive index anisotropy of compounds (1-A) and (1-B). 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2 in which at least one hydrogen in each of rings A ¹¹ to A ¹³ is replaced with fluorine; ,5-diyl is effective in developing a large dielectric anisotropy, and 1,4-cyclohexylene, tetrahydropyran-2,5-diyl ring is compound (1-A) or (1 - Contributes to good compatibility expression of B).
the linking groups Z ¹¹ , Z ¹² and Z ¹³ are each a single bond, -CH ₂ CH ₂ -, -CH=CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ - , -CF=CF-, -( _CH2 ) _3- O-, -O-( _CH2 ) _3- , -( _CH2 ) ₂ - _CF2O- , _-OCF2- ( _CH2 ) _2- or When -(CH ₂ ) ₄ -, the viscosity of compound (1-A) or (1-B) is small. Further, when the bonding groups Z ¹¹ , Z ¹² and Z ¹³ are each a single bond, -(CH ₂ ) ₂ -, -CF ₂ O-, -OCF ₂ - or -CH=CH-, the compound (1-A ) or (1-B) is further reduced in viscosity. When the bonding groups Z ¹¹ , Z ¹² and Z ¹³ are each -C≡C-, the compound (1-A) or (1-B) has a large refractive index anisotropy. When the bonding groups Z ¹¹ , Z ¹² and Z ¹³ are -COO- or -CF ₂ O- respectively, the compound (1-A) or (1-B) has a large dielectric anisotropy. Z ¹¹ , Z ¹² and Z ¹³ are each a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, or -(CH ₂ ) ₄ - In some cases, compound (1-A) or (1-B) is relatively chemically stable and hardly deteriorates.
In general, when the refractive index anisotropy or the dielectric anisotropy is large, the driving voltage of the liquid crystal element according to the embodiment of the present invention tends to be low, and the response speed is high when the viscosity is low.
When X ¹¹ is fluorine, chlorine, -SF ₅ , -CHF ₂ , -CF ₃ , -CH ₂ F, -OCF ₃ , -OCHF ₂ or -OCH ₂ F, the dielectric constant difference of compound (1-A) Highly directional. It is chemically stable when X ¹¹ is fluorine or —OCF ₃ .
both L ¹¹ and L ¹² are fluorine and X ¹¹ is fluorine, chlorine, -SF ₅ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF _2, or -OCH ₂ F , the dielectric anisotropy of the compound (1-A) is very large. Also, when L ¹¹ is fluorine, L ¹² is hydrogen, and X ¹¹ is —CF ₃ or —OCF ₃ , both L ¹¹ and L ¹² are fluorine and X ¹¹ is —CF ₃ or —OCF ₃ or when all of L ¹¹ , L ¹² and X ¹¹ are fluorine, the compound (1-A) has a large dielectric anisotropy, a wide liquid crystal phase temperature range, and chemical stability. Not prone to deterioration.
Further, when both L ¹³ and L ¹⁴ are fluorine and R ¹² is alkoxy, the dielectric anisotropy of the compound (1-B) is large and the temperature range of the liquid crystal phase is wide. Further, when L ¹³ is fluorine and R ¹² is alkyl, the compound (1-B) has a large dielectric anisotropy, is chemically stable, and hardly deteriorates.
The larger m+n, the higher the clearing point of the compound, and the smaller m+n, the lower the melting point of compound (1-A).

1.3.3 Other Achiral Components For the purpose of optimizing the properties of the liquid crystal composition according to the embodiment of the present invention, a compound represented by the following formula (1-C) is optionally added as an achiral component. can be used.

In the above formula (1-C),
R ¹¹ and R ¹² are each independently hydrogen, alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, or alkoxy having 1 to 8 carbon atoms;
Z ¹¹ and Z ¹² are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ - , -CH=CH-, -CF=CF-, or -C≡C-;
Ring A ¹¹ and Ring A ¹² are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3-dioxane-2, 5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
p is 1, 2, or 3;

The compound (1-C) is a compound with small dielectric anisotropy and exhibits low viscosity. The general relationship between the type of combination of terminal groups R ¹¹ and R ¹² , ring A ¹¹ and A ¹² , and bonding groups Z ¹¹ and Z ¹² of compound (1-C) and physical properties is shown in Compound (1-A) and (1-B).
As for p, when p is 1, the clearing point is low and the viscosity is low. When p is 2, the clearing point and viscosity are well balanced, and when p is 3, the clearing point is high.

As the compound represented by the above formula (1-C), any one of the compounds represented by the following formulas (1-C-01) to (1-C-14) is particularly preferred.

In formulas (1-C-01) to (1-C-14), R ¹¹ and R ¹² are each independently hydrogen, alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, or 1-8 alkoxy, A ¹¹ and A ¹² are each independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; (F) is hydrogen or fluorine.

2. Monomer/liquid crystal mixture containing liquid crystal composition and polymerizable monomer, and polymer/liquid crystal composite material A second aspect of the present invention is a liquid crystal composition having a chiral nematic phase or an optically isotropic liquid crystal phase and polymerizable It is a mixture containing monomers. In this specification, the term "polymerizable monomer" is a concept including macromonomers and oligomers.
When the liquid crystal composition and a monomer/liquid crystal mixture containing a polymerizable monomer are used as a material for a liquid crystal element having a light control layer such as a light control window, it can be driven at a lower voltage and has higher contrast characteristics. A liquid crystal element having It is preferable to use the monomer/liquid crystal mixture according to the embodiment of the present invention in order to control the structure of the transparent material that will be part of the light control layer of the liquid crystal element described later according to the purpose.
A third aspect of the present invention is a polymer/liquid crystal composite material, which can be produced, for example, by subjecting a monomer/liquid crystal mixture containing the liquid crystal composition of the second aspect of the present invention and a polymerizable monomer to a polymerization reaction. . A polymer/liquid crystal composite material according to an embodiment of the present invention preferably has a chiral nematic phase or an optically isotropic liquid crystal phase. The polymer/liquid crystal composite material is not particularly limited as long as it is a composite material containing both a liquid crystal composition and a polymer compound. The molecules may be in a phase-separated state from the liquid crystal composition.

An optically isotropic polymer/liquid crystal composite material according to an embodiment of the present invention can develop an optically isotropic liquid crystal phase in a wide temperature range. In addition, since a low driving voltage and an extremely fast response speed can be realized, it can be suitably used for a liquid crystal element for display and the like based on these effects.
A polymer/liquid crystal composite material exhibiting a chiral nematic phase according to a preferred embodiment of the present invention can exhibit a chiral nematic phase in a wide temperature range. In addition, sufficient contrast can be obtained between opacity and transparency due to light scattering when a voltage is applied and when no voltage is applied.

2.1 Polymerization Conditions for Producing Polymer/Liquid Crystal Composite Material The polymer/liquid crystal composite material of the present invention can be produced by mixing a liquid crystal composition and a pre-polymerized polymer. Low-molecular-weight monomers, macromonomers, oligomers, etc. (hereinafter collectively referred to as "polymerizable monomers"), which are used as polymer materials, are mixed with a liquid crystal composition, and then the mixture is subjected to a polymerization reaction. preferably.
A mixture comprising the liquid crystal composition of the second aspect of the present invention and a polymerizable monomer is also referred to herein as a "monomer/liquid crystal mixture". The "monomer/liquid crystal mixture" may optionally include polymerization initiators, curing agents, catalysts, stabilizers, dichroic dyes (merocyanines, styryls, azos, azomethines, azoxys, quinophthalones, anthraquinone-based, tetrazine-based, etc.), photochromic compounds, etc., may be included as long as the effects of the present invention are not impaired. For example, a monomer/liquid crystal mixture according to embodiments of the present invention may optionally contain a polymerization initiator in an amount of 0.1 to 20 parts by weight of the polymerizable monomer.

When preparing a polymer/liquid crystal composite with optical isotropy, polymerization in a monomer/liquid crystal mixture comprising a liquid crystal composition and a polymerizable monomer converts the monomer/liquid crystal mixture into a non-liquid crystal isotropic phase or It is preferably carried out in an optically isotropic liquid crystal phase. That is, the polymerization temperature is preferably a temperature at which the polymer/liquid crystal composite exhibits high transparency and isotropy. More preferably, the polymerization is terminated at a temperature at which the mixture of the polymerizable monomer and the liquid crystal composition develops a non-liquid crystal isotropic phase or a blue phase and in a non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase. That is, after polymerization, the polymer/liquid crystal composite material preferably does not scatter light on the longer wavelength side than visible light and exhibits an optically isotropic state at a polymerization temperature.
Further, when the polymer/liquid crystal composite material according to the embodiment of the present invention is used as the light control layer, light can be applied while a voltage is applied between the transparent conductive films during the polymerization reaction.

2.2 Raw Material of Polymer Constituting Polymer/Liquid Crystal Composite Material As a raw material of polymer constituting the polymer/liquid crystal composite material according to the embodiment of the present invention, a polymerizable monomer such as a low-molecular-weight monomer , macromonomers, oligomers can be used. Moreover, the resulting polymer preferably has a three-dimensional crosslinked structure, and for this reason, it is preferable to use a polyfunctional monomer having two or more polymerizable functional groups as the raw material of the polymer. Although the polymerizable functional group is not particularly limited, examples thereof include acrylic group, methacrylic group, glycidyl group, epoxy group, oxetanyl group, vinyl group, etc. From the viewpoint of polymerization rate, acrylic group and methacrylic group are preferred. When 10% by weight or more of the monomer having two or more polymerizable functional groups is contained in the raw material of the polymer, the polymer/liquid crystal composite material according to the embodiment of the present invention exhibits high transparency and It is preferable because it facilitates isotropy.
Moreover, in order to obtain a suitable composite material, the polymer preferably has a mesogenic site, and a monomer having a mesogenic site can be used as a raw material for the polymer in part or in its entirety.

2.2.1 Monomers with mesogenic moieties (monoreactive, direactive and trireactive monomers)
The monoreactive, direactive, or trireactive monomer having a mesogenic moiety is not particularly limited in terms of structure. can.

In formulas (M1) to (M3), R ^MA is hydrogen, halogen, —CF ₃ , —OCF ₃ , —C≡N, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or 1 carbon atom. -20 alkoxy, or alkoxycarbonyl having 2 to 20 carbon atoms. A preferred ^RMA is alkyl of 1 to 20 carbons or alkoxy of 1 to 20 carbons.
Each ^RMB is independently a polymerizable group (M3-1) to (M3-7).

Here, each R ^d in groups (M3-1) to (M3-7) is independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms, and at least one hydrogen in these alkyl is halogen. may be replaced. Preferred ^Rd are hydrogen, fluorine and methyl.
Moreover, the group (M3-2), the group (M3-3), the group (M3-4) and the group (M3-7) are preferably polymerized by radical polymerization. Group (M3-1), group (M3-5) and group (M3-6) are preferably polymerized by cationic polymerization. Since both are living polymerizations, the polymerization starts when a small amount of radical or cationic active species is generated in the reaction system. A polymerization initiator can be used for the purpose of accelerating the generation of active species. For example, light or heat can be used to generate active species.
Each A ^M is independently an aromatic or non-aromatic 5-membered ring, 6-membered ring or condensed ring having 9 or more carbon atoms, and —CH ₂ — in the ring is —O—, —S -, -NH-, or -NCH ₃ -, where -CH= in the ring may be replaced by -N=, hydrogen atoms in the ring are halogen, and alkyl having 1 to 5 carbon atoms, or halogenated alkyl may be replaced with
Specific examples of preferred ^AM are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, 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 is not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.
Each Y ^M is independently a single bond or an alkylene having 1 to 20 carbon atoms, and in these alkylenes, at least one —CH ₂ — is —O—, —S—, —CH═CH—, —C≡ It may be replaced with C-, -COO-, or -OCO-, but two oxygen atoms are not adjacent as in -O-O-. Preferred Y ^M are a single bond, —(CH ₂ ) _m2 —, —O(CH ₂ ) _m2 —, and —(CH ₂ ) _m2 O— (where m2 is an integer from 1 to 20). be.
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 m3 is an integer of 1 to 20).
Preferred Z ^M is a single bond, -(CH ₂ ) _m3 -, -O(CH ₂ ) _m3 -, -(CH ₂ ) _m3 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- (wherein m3 is an integer of 1 to 20).
Each m1 is independently an integer of 0 to 2. When the sum of m1 is 1, it is a bicyclic compound having two rings such as a 6-membered ring. When the sum of m1 is 2 or 3, they are tricyclic and tetracyclic compounds, respectively. When there are multiple m1s, two or more A ^M or two or more Z ^M may be the same or different. The same is true for ^RMB and ^YM .

The compounds represented by the formulas (M1) to (M3) have similar properties even if they contain isotopes such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance ratio, so they are preferably used. can.
More preferred examples of compounds (M1) to (M3) are the following formulas (M1-1) to (M1-16), (M2-1) to (M2-14), and (M3-1) to (M3- It is a compound represented by 3). In these compounds, the meanings of R ^MA , R ^MB , Z ^M , ^AM , and Y ^M are the same as those of formulas (M1) and (M2) described in aspects of the present invention.

下記のメソゲン部位を有さないモノマー、およびメソゲン部位を持つモノマー（Ｍ１）、および（Ｍ２）以外の重合性化合物を必要に応じて使用することができる。The following partial structures of compounds (M1-1) to (M1-16), (M2-1) to (M2-14), and (M3-1) to (M3-3) are explained. Partial structure (a1) represents 1,4-phenylene in which at least one hydrogen may be replaced by fluorine or methyl. Partial structure (a2) represents fluorene in which hydrogen at position 9 may be replaced with methyl.

Polymerizable compounds other than the following monomers having no mesogenic site and monomers (M1) and (M2) having a mesogenic site can be used as necessary.

2.2.2 Monomers having a polymerizable functional group that does not have a mesogenic moiety Examples of monomers that have a polymerizable functional group that does not have a mesogenic moiety include linear or branched acrylates having 1 to 30 carbon atoms. , linear or branched methacrylates having 1 to 30 carbon atoms, linear or branched diacrylates having 1 to 30 carbon atoms, and linear or branched dimethacrylates having 1 to 30 carbon atoms, and having three or more polymerizable functional groups Examples of monomers having triacrylate, trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, di(pentaerythritol) pentaacrylate, and di(pentaerythritol) hexaacrylate, etc. It is not limited to these.

2.3 Polymerization Initiator The polymerization reaction in the production of the polymer constituting the polymer/liquid crystal composite material according to the embodiment of the present invention is not particularly limited. done.
Examples of photoradical polymerization initiators that can be used in photoradical polymerization include DAROCUR 1173 and 4265 (both trade names, BASF Japan Ltd.), IRGACURE 184, 369, 500, 651, 784. , 819, 907, 1300, 1700, 1800, 1850, and 2959 (all trade names, BASF Japan Ltd.), and the like.
Examples of preferred thermal radical polymerization initiators that can be used in the thermal radical polymerization are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate. , t-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbohydrate Nitrile (ACN) and the like.
Examples of photocationic polymerization initiators that can be used in photocationic polymerization include diaryliodonium salts (hereinafter referred to as "DAS") and triarylsulfonium salts (hereinafter referred to as "TAS"). Examples of specific trade names of photocationic polymerization initiators include Cyracure UVI-6990, Cyracure UVI-6974, Cyracure UVI-6992 (each trade name, UCC Corporation), Adeka Optomer SP-150, SP-152, SP-170, SP-172 (trade name, ADEKA Corporation), Rhodorsil Photoinitiator 2074 (trade name, Rhodia Japan Co., Ltd.), IRGACURE 250 (trade name, BASF Japan Ltd.) ), and UV-9380C (trade name, GE Toshiba Silicone Co., Ltd.).

2.4 Curing Agent, etc. In the production of the polymer constituting the polymer/liquid crystal composite material according to the embodiment of the present invention, in addition to the monomers and the like and the polymerization initiator, one or more other suitable Components such as one or more selected from curing agents, catalysts, stabilizers, chain transfer agents, photosensitizers, dye crosslinkers, 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 latent epoxy resin curing agents include amine-based curing agents, novolac resin-based curing agents, imidazole-based curing agents, and acid anhydride-based curing agents.
Further, a curing accelerator may be further used for accelerating the curing reaction between the polymerizable compound having glycidyl, epoxy, or oxetanyl and the curing agent. Curing accelerators include, for example, benzyldimethylamine, tris(dimethylaminomethyl)phenol, tertiary amines such as dimethylcyclohexylamine, 1-cyanoethyl-2-ethyl-4-methylimidazole, 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 the like and organic acid salts thereof Examples include diazabicycloalkenes, quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide, boron trifluoride, and boron compounds such as triphenylborate. These curing accelerators can be used alone or in combination of two or more.
It is also preferred to add stabilizers, for example to prevent undesired polymerization during storage. As stabilizers it is possible to use all compounds known to the person skilled in the art. Representative examples of stabilizers include 4-ethoxyphenol, hydroquinone, butylated hydroxytoluene (BHT), and the like.

2.5 Content of Polymerizable Monomer, Etc. in Monomer/Liquid Crystal Mixture The content of the polymerizable monomer in the monomer/liquid crystal mixture according to the embodiment of the present invention can be adjusted according to the intended use. When used as a material for forming a light-modulating layer of a liquid crystal device, the polymerizable monomer is 0.00 in the monomer/liquid crystal mixture in order to obtain a sufficient contrast between opacity and transparency due to light scattering. It is preferably contained in the range of 1 to 50% by weight, more preferably in the range of 0.1 to 40% by weight, and more preferably in the range of 0.1 to 10% by weight. .
The content of the liquid crystal composition in the polymer/liquid crystal composite material according to the embodiment of the present invention varies depending on the purpose of use, but the range in which the polymer/liquid crystal composite material can exhibit optical isotropy or the composite material is required. It is preferable that the content is as low as possible as long as the helical pitch can be expressed. ) and high contrast.

2.6 Other Components The polymer/liquid crystal composite material according to the embodiment of the present invention may contain, for example, a dichroic dye and a photochromic compound within a range that does not impair the effects of the present invention.

3 Liquid crystal element 3.1 Liquid crystal element using optically isotropic liquid crystal composition A liquid crystal element driven by an optically isotropic liquid crystal phase, including an optically isotropic one, is sometimes called a "liquid crystal medium" together with a composition and a polymer/liquid crystal composite material. .
As an example of the structure of a liquid crystal display element using an optically isotropic liquid crystal composition, as shown in FIG. Arranged structures can be mentioned. When there is a potential difference between the electrodes 1 and 2, it is possible to provide a state in which electric fields exist in two directions, upward and downward, on the comb-shaped electrode substrate as shown in FIG.

3.2 Liquid Crystal Element Using Liquid Crystal Composition Showing Chiral Nematic Phase A fifth aspect of the present invention is the liquid crystal composition or polymer/liquid crystal composite material according to the embodiment of the present invention showing a chiral nematic phase. It is a liquid crystal element that uses a material as a light modulating material.
A liquid crystal device according to an embodiment of the present invention has two substrates each having an electrode layer, at least one of which is transparent, and a light control layer supported between the substrates. This light control layer is made of the polymer/liquid crystal composite material described above. Here, the polymer contained in the polymer/liquid crystal composite material is preferably transparent. In addition, the polymer/liquid crystal composite material preferably forms a continuous layer, which is important in forming an optical interface by forming a disordered state of the liquid crystal molecules to develop light scattering.
The polymer in the polymer in the light control layer/polymer in the liquid crystal composite material is composed of the polymer of the polymerizable monomer contained in the monomer/liquid crystal mixture, and is dispersed in the form of fibers or particles. It may be in the form of a film in which the polymer/liquid crystal composite material is dispersed in the form of droplets, or in the form of a gel having a three-dimensional network structure.
A transparent or opaque electrode may be appropriately arranged on the entire surface or part of the substrate according to the purpose. At least one of the substrates is transparent, but complete transparency is not essential. If the liquid crystal element is to be used to act on light passing from one side of the liquid crystal element to the other, both substrates are given suitable transparency.
The substrate used in the liquid crystal device may be a rigid material such as glass or metal, or a flexible material such as a plastic film. In the liquid crystal element, two substrates can be opposed to each other with an appropriate gap therebetween.
Further, an alignment film such as polyimide may be disposed on the entire surface or part of at least one of the substrates as required. Between the two substrates, a spacer for maintaining a gap can be interposed, as in the well-known liquid crystal element.

Among the liquid crystal elements according to the embodiments of the present invention, a liquid crystal element driven in reverse mode can be manufactured, for example, as follows. That is, the monomer/liquid crystal mixture is interposed between two substrates, at least one of which has an electrode layer and is transparent, and the monomer is irradiated with ultraviolet rays through the transparent substrate or by heating the transparent substrate. / By polymerizing a polymerizable monomer contained in a liquid crystal mixture, a liquid crystal device having a light control layer composed of a polymer and a liquid crystal compound can be produced.
A schematic diagram is shown in FIG. 3 as an example of a reverse mode driven liquid crystal element. FIG. 3(a) shows a state in which no voltage is applied, the orientation of the liquid crystal compound is planar, and the panel is transparent because light is transmitted therethrough. FIG. 3(b) shows the state of voltage application, the orientation of the liquid crystal compound is homogeneous, and the panel becomes cloudy because the light is scattered.

Among the liquid crystal elements according to the embodiments of the present invention, a normal mode liquid crystal element can be manufactured, for example, as follows. That is, the above-described monomer/liquid crystal mixture is interposed between two substrates having electrode layers and at least one of which is transparent, and ultraviolet rays are passed through the transparent substrate while applying a saturation voltage specific to the liquid crystal compound. or by heating a transparent substrate to polymerize the polymerizable monomer contained in the monomer/liquid crystal mixture, thereby producing a liquid crystal device having a light control layer composed of a polymer and a liquid crystal compound. be able to.
A schematic diagram is shown in FIG. 4 as an example of a liquid crystal element driven in normal mode according to the present invention. FIG. 4A shows the state where no voltage is applied, the orientation of the liquid crystal compound is focal conic, and the panel becomes cloudy because the light is scattered. FIG. 4(b) shows the voltage application state, the orientation of the liquid crystal compound is homeotropic, and the panel becomes transparent because light is transmitted.

The method of interposing the monomer/liquid crystal mixture, which is the material for forming the light control layer, between the two substrates is not particularly limited, and the monomer/liquid crystal mixture may be injected between the substrates by a known injection technique. For example, one substrate may be uniformly coated using a suitable solution coater, spin coater, or the like, and then the other substrate may be overlaid and pressure-bonded.
The layer thickness of the light-scattering light-modulating layer in the liquid crystal device of the present invention can be adjusted according to the purpose of use. In order to obtain , the layer thickness (substrate spacing) is preferably in the range of 2 to 40 μm, particularly preferably in the range of 6 to 25 μm.
The liquid crystal device according to the embodiment of the present invention can be used as a light control window, a light modulation device, and the like in various applications such as architectural applications such as indoor interiors and automobile applications such as automobile leafs.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by weight".

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 an optically isotropic phase in which two or more colors of diffracted light are not observed. represents the liquid crystal phase of In this specification, the IN phase transition point is sometimes referred to as the NI point. The IN ^* phase transition point is sometimes called the N ^* -I point. The I-BP phase transition point is sometimes called the BP-I point.
In the examples of the present specification, unless otherwise specified, the measurement and calculation of physical properties were performed according to the method described in Standard of Electronic Industries Association of Japan, EIAJ ED-2521A. Specific measurement methods, calculation methods, etc. are as follows.

1) IN phase transition point (T _NI )
Place the sample on the hot plate of a melting point measuring apparatus equipped with a polarizing microscope. appeared a chiral nematic phase or an optically anisotropic phase. The phase transition temperature in the process was measured, then heated at a rate of 1° C./min and the phase transition temperature in the process was measured. In the optically isotropic liquid crystal phase, when it was difficult to determine the phase transition point in a dark field under crossed Nicols, the phase transition temperature was measured with the polarizing plate shifted from the crossed Nicols state by 1 to 10°.

2) Refractive index (n∥ and n⊥; measured at 25°C)
The measurement was performed with an Abbe refractometer having a polarizing plate attached to an eyepiece using light with a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index (n∥) was measured when the direction of polarization was parallel to the rubbing direction. The refractive index (n⊥) was measured when the polarization direction was perpendicular to the rubbing direction.

3) Pitch (P; measured at 25°C; nm)
The pitch length was measured using selective reflection (liquid crystal handbook, page 196, published in 2000, Maruzen). A relational expression <n>p/λ=1 holds for the selective reflection wavelength λ. Here, <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 was measured with a microscopic spectrophotometer (Otsuka Electronics Co., Ltd., trade name FE-3000). The pitch was obtained by dividing the obtained reflection wavelength by the average refractive index.
The pitch of cholesteric liquid crystals that reflect wavelengths in the long or short wavelength region of visible light, and the pitch of cholesteric liquid crystals that have been difficult to measure, is obtained by adding a chiral compound at a concentration that has a selective reflection wavelength in the visible light region ( concentration C′), and the selective reflection wavelength (λ′) is measured. '/C).

4) HTP (helical twist power) (measured at 25° C.; μm ⁻¹ )
Using the average refractive index <n> obtained by the above method and the pitch value, HTP is given by the following equation. HTP=<n>/(λ×C). λ indicates the selective reflection wavelength (nm), and C indicates the concentration (wt%) of the chiral compound.

5) Voltage holding ratio (VHR; measured at 60°C; %)
The TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. The device was sealed with a UV curable adhesive after the sample was injected. A pulse voltage (60 μs at 5 V) was applied to the TN element to charge it, and the attenuating voltage was measured with a high-speed voltmeter for 16.7 ms. The area A was obtained. Area B was the area when there was no attenuation. The voltage holding ratio (%) was expressed as a percentage of the area A with respect to the area B.

6) Measurement of the transmitted light intensity of the cell and calculation of the transmittance of the cell The cell was installed in a UV-visible spectrophotometer V650DS manufactured by JASCO Corporation so that the light source light was perpendicular to the cell surface. Transmitted light intensity was measured. The bandwidth of incident light at that time was 5 nm. The transmittance/% of the cell was calculated as the transmitted light intensity of the cell to be measured/(the light intensity measured when the cell to be measured was not placed in the spectrometer)×100. Using an electric field application unit and a bipolar power source, the transmitted light intensity of the cell with a voltage applied to the cell and the transmitted light intensity of the cell with no voltage applied were measured. Waveform generator 33210A manufactured by Agilent was used as the electric field application unit, and nf ELECTRONIC INSTRUMENTS 4010 manufactured by NF was used as the bipolar power supply.

7) Calculation of Contrast Ratio Contrast ratio is the ratio of transmitted light intensity under specific conditions to transmitted light intensity under different conditions.

The proportions (percentages) of components or liquid crystal compounds are weight percentages (% by weight) based on the total weight of the liquid crystal compounds. The composition is prepared by weighing components such as a liquid crystal compound and then mixing. Therefore, it is easy to calculate the weight percentages of the components.

[Example 1]
<Synthesis of compound (K101)>

(Compound (K1-1) in which Rodk1=Rod1-1C, nk1=nk2=0, and R ^k2 =C ₅ H ₁₁ )
Compound (K101) was synthesized according to the scheme below.

(First step) Synthesis of compound (103) Under nitrogen atmosphere, compound (102) (38.6 g, 326 mmol) and triethylamine (36.4 g, 360 mmol) were prepared in toluene (150 mL), and compound (103) was obtained at room temperature. 101) (25.0 g, 163 mmol) was slowly added dropwise, and the mixture was stirred at that temperature for 1 hour. The reaction mixture was filtered to remove insolubles, poured into water, toluene (100 mL) was added, washed twice with water, and then the organic phase was concentrated, and the residue was subjected to silica gel column chromatography (developing solvent: toluene/ The compound (103) (15.7 g, 163 mmol) was obtained by isolation and purification with ethyl acetate=1/1).

(Second step) Synthesis of compound (104) Under a nitrogen atmosphere, a toluene (150 mL) solution of compound (103) (29.6 g, 93.5 mmol) obtained in the previous step and anthracene (25 g, 140 mmol) was heated at 110°C for 3 hours. The mixture was heated and stirred for days. After removing the remaining anthracene by dissolving the reaction solution, the organic phase was concentrated, and the residue was isolated and purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 4/1) to obtain a white crystal compound. (104) (46.2 g, 93.5 mmol) was obtained.

(3rd step) Synthesis of compound (105) Under a nitrogen atmosphere, prepare a mixed solution of compound (104) (20 g, 40.4 mmol) obtained in the previous step in THF (100 mL)/water (100 mL), and bring it to room temperature. A methanol solution of lithium hydroxide (2.91 g, 121 mmol) was slowly added thereto, and the mixture was stirred at that temperature for 24 hours. The reaction mixture was cooled to 5°C, slowly added with 1N-HCl solution until the pH reached 4, poured into water, extracted with diethyl ether (300 mL), and washed twice with water. The organic phase was concentrated, and the residue was isolated and purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate=2/1) to obtain compound (105) (8.50 g, 28.9 mmol) as white crystals. .

(Step 4) Synthesis of compound (K101) Under a nitrogen atmosphere, a solution of phenol derivative (106) (7.37 g, 29.9 mmol) in dichloromethane (5 mL) was cooled to -10°C to obtain N,N'-dicyclohexylcarbodiimide ( 6.17 g, 29.9 mmol), 4-dimethylaminopyridine (1.00 g, 8.15 mmol), and the carboxylic acid derivative (105) obtained in the previous step (4.00 g, 13.6 mmol) were added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was filtered, poured into water, dichloromethane (50 mL) was added, and washed twice with aqueous sodium bicarbonate and twice with water. After concentrating the organic phase, the residue was isolated and purified by silica gel column chromatography (developing solvent: toluene) to obtain compound (K101) (6.30 g, 8.39 mmol). The melting point of this compound was 85°C.
¹ H-NMR (CDCl ₃ , ppm): δ 0.932-0.985 (6H, t), 1.37-1.43 (8H, m), 1.66-1.71 (4H, m), 2.66-2.69 (4H, t), 3.93 (2H, s), 5.07(2H, s), 7.04-7.07(4H, d), 7.24-7.31(8H, m), 7.46-7.51(8H, m), 7.58-7.60(4H, d).

（化合物（Ｋ１－１）において、Ｒｏｄｋ１＝Ｒｏｄ１－１Ｇであり、ｎｋ１＝ｎｋ２＝０、Ｒ^ｋ２＝Ｃ_５Ｈ_１１である化合物）
実施例１と同様の方法で、化合物（１０６）の代わりに下記の化合物（１０７）を使用して、化合物（Ｋ１０２）（2.40g, 2.66mmol）を得た。この化合物の融点は１８２℃であった。

^１Ｈ－ＮＭＲ（ＣＤＣｌ_３、ｐｐｍ）： δ0.885-0.914(6H, t), 1.02-1.10(4H, m), 1.20-1.35(18H, m), 1.45-1.55(4H, m), 1.86-1.93(8H, m), 2.47-2.58(2H, tt), 3.88(2H, s), 5.03(2H, s), 7.00-7.02(4H, d), 7.21-7.22(4H, m), 7.26-7.28(4H, d), 7.42-7.48(8H, m), 7.53-7.55(4H, d)．[Example 2]
<Synthesis of compound (K102)>

(Compound (K1-1) in which Rodk1=Rod1-1G, nk1=nk2=0, and R ^k2 =C ₅ H ₁₁ )
Compound (K102) (2.40 g, 2.66 mmol) was obtained in the same manner as in Example 1 using compound (107) below instead of compound (106). The melting point of this compound was 182°C.

¹ H-NMR (CDCl ₃ , ppm): δ 0.885-0.914 (6H, t), 1.02-1.10 (4H, m), 1.20-1.35 (18H, m), 1.45-1.55 (4H, m), 1.86 -1.93(8H, m), 2.47-2.58(2H, tt), 3.88(2H, s), 5.03(2H, s), 7.00-7.02(4H, d), 7.21-7.22(4H, m), 7.26 -7.28 (4H, d), 7.42-7.48 (8H, m), 7.53-7.55 (4H, d).

（化合物（Ｋ１－１）において、Ｒｏｄｋ１＝Ｒｏｄ１－１Ｄであり、ｎｋ１＝ｎｋ２＝０、Ｒ^ｋ２＝Ｃ_５Ｈ_１１である化合物）
実施例１と同様の方法で、化合物（１０６）の代わりに下記の化合物（１０８）を使用して、化合物（Ｋ１０３）（9.04g, 12.0mmol）を得た。この化合物は常温でアモルファス状態であった。

^１Ｈ－ＮＭＲ（ＣＤＣｌ_３、ｐｐｍ）： δ0.879-0.907(6H, t), 0.990-1.06(4H, m), 1.18-1.33(18H, m), 1.38-1.43(4H, m), 1.84-1.86(8H, d), 2.40-2.48(2H, tt), 3.82(2H, s), 4.98(2H, s), 6.84-6.86(4H, d), 7.16-7.20(8H, m), 7.38-7.40(2H, d), 7.42-7.43(2H, m)．[Example 3]
<Synthesis of compound (K103)>

(Compound (K1-1) in which Rodk1=Rod1-1D, nk1=nk2=0, and R ^k2 =C ₅ H ₁₁ )
Compound (K103) (9.04 g, 12.0 mmol) was obtained in the same manner as in Example 1 using compound (108) below instead of compound (106). This compound was in an amorphous state at room temperature.

¹ H-NMR (CDCl ₃ , ppm): δ 0.879-0.907 (6H, t), 0.990-1.06 (4H, m), 1.18-1.33 (18H, m), 1.38-1.43 (4H, m), 1.84 -1.86(8H, d), 2.40-2.48(2H, tt), 3.82(2H, s), 4.98(2H, s), 6.84-6.86(4H, d), 7.16-7.20(8H, m), 7.38 -7.40(2H, d), 7.42-7.43(2H, m).

[Example 4-1]
A liquid crystal composition NLC-A was prepared by mixing the liquid crystal compounds shown in the figure below in the following proportions.

This liquid crystal composition NLC-A had a phase transition temperature (° C.) of N 79.7 I and an average refractive index <n> of 1.56.

The compound (K101) (2.00% by weight) obtained in Example 1 was heated and dissolved in liquid crystal composition NLC-A (98.0% by weight) at 100° C. to obtain liquid crystal composition CLC-A1. rice field. The phase transition temperature (° C.) of this liquid crystal composition CLC-A1 was N ^* 79.1I.
At this time, the heating time required to obtain the completely dissolved liquid crystal composition CLC-A1 was 2 minutes. As a result, it was found that the compound (K101) exhibits a very high solubility.
The selective reflection wavelength (λ) of the liquid crystal composition CLC-A1 was 484.0 (nm), and the HTP of the compound (K101) calculated from these values was 161 (μm ^-1 ). Further, when the VHR of the liquid crystal composition CLC-A1 was measured, it was 96.1%. As a result, it was found that the composition CLC-A1 exhibited a high voltage holding ratio.

[Example 4-2]
A liquid crystal composition NLC-B was prepared by mixing the liquid crystal compounds shown in the figure below in the following proportions.

The liquid crystal composition NLC-B had a phase transition temperature (° C.) of N 87.9 I and an average refractive index <n> of 1.56.

The compound (K101) (4.80% by weight) obtained in Example 1 was completely dissolved in the liquid crystal composition NLC-B (95.2% by weight) by heating and stirring at 100°C for 2 minutes to obtain a liquid crystal composition. The product CLC-B1 was obtained.
The phase transition temperature (° C.) of this liquid crystal composition CLC-B1 was N ^* 79.1BP79.2I.

[Example 4-3]
Preparation of monomer/liquid crystal mixture As a mixture of liquid crystal composition and polymerizable monomer, 89.2% by weight of liquid crystal composition CLC-B1, 5.4% by weight of n-hexadecyl acrylate (C16A), compound (MC3-12 ) was mixed with 0.4% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator to prepare a liquid crystal composition MLC-B1. The phase transition temperature (° C.) of this liquid crystal composition MLC-B1 was N ^* 51.1 BP 54.6 I, I 53.3 BP 49.7 N ^* .

[Example 4-4]
Preparation of polymer/liquid crystal composite material Liquid crystal composition MLC-B1 was sandwiched between a comb-shaped electrode substrate not subjected to alignment treatment and a counter glass substrate (non-electrode-provided) (cell thickness: 8 μm). was heated to a blue phase of 52.0°C. In this state, ultraviolet light (ultraviolet light intensity of 23 mWcm ⁻² (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer/liquid crystal composite material PSBP-B1 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 rightward from the left connection electrode portion and electrodes 2 extending leftward from the right connection electrode portion. . Therefore, when there is a potential difference between the electrodes 1 and 2, on the comb-shaped electrode substrate as shown in FIG. A state in which an electric field is present can be provided.

[Example 4-5]
The cell in which the polymer/liquid crystal composite material PSBP-B1 obtained in Example 4-4 was sandwiched was set in the optical system shown in FIG. 2, and electro-optical properties were measured. The measurement optical system of FIG. 2 includes a light source 3, a polarizer 4, a comb-shaped electrode 5, an analyzer 6, and a light receiver 7. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) was used as the light source 3, the incident angle to the cell was set to be perpendicular to the cell surface, and the linear direction of the comb-shaped electrode 5 was aligned with the Polarizer 4 and Analyzer 6 polarizing plates. The cell was set in the optical system so that each angle was 45°. The relationship between applied voltage and transmittance was investigated at room temperature. When a rectangular wave of 68.4 V was applied, the transmittance became 89.7% and the transmitted light intensity was saturated. The contrast showed a very high value of 1614.

[Example 5-1]
The compound (K102) (2.00% by weight) obtained in Example 2 was heated and dissolved in liquid crystal composition NLC-A (98.0% by weight) at 100° C. to obtain liquid crystal composition CLC-A2. rice field. The phase transition temperature (° C.) of this liquid crystal composition CLC-A2 was N ^* 79.1I.
At this time, the heating time required to obtain the completely dissolved liquid crystal composition CLC-A2 was 3 minutes. As a result, it was found that the compound (K102) exhibits a very high solubility.
The selective reflection wavelength (λ) of the liquid crystal composition CLC-A2 was 560 (nm). The HTP of compound (K102) calculated from these values was 139 (μm ⁻¹ ). Further, when the VHR of the liquid crystal composition CLC-A2 was measured, it was 95.6%. As a result, it was found that the composition CLC-A2 exhibited a high voltage holding ratio.

[Example 5-2]
The compound (K102) (4.80% by weight) obtained in Example 2 was completely dissolved in the liquid crystal composition NLC-B (95.2% by weight) by heating and stirring at 100°C for 2 minutes to obtain a liquid crystal composition. The product CLC-B2 was obtained.
The phase transition temperature (° C.) of this liquid crystal composition CLC-B2 was N ^* 83.5BP83.7I.

[Example 5-3]
Preparation of monomer/liquid crystal mixture As a mixture of liquid crystal composition and polymerizable monomer, 89.2% by weight of liquid crystal composition CLC-B2, 5.4% by weight of n-hexadecyl acrylate (C16A), compound (MC3-12 ) was mixed with 0.4% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator to prepare a liquid crystal composition MLC-B2. The phase transition temperature (° C.) of this liquid crystal composition MLC-B2 was N ^* 55.4 BP 55.5 I, I 55.6 BP 54.7 N ^* .

[Example 5-4]
Preparation of polymer/liquid crystal composite material Liquid crystal composition MLC-B2 was sandwiched between a comb-shaped electrode substrate not subjected to alignment treatment and a counter glass substrate (non-electrode-provided) (cell thickness: 8 μm). was heated to a blue phase of 55.4°C. In this state, ultraviolet light (ultraviolet light intensity of 23 mWcm ⁻² (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer/liquid crystal composite material PSBP-B2 thus obtained maintained an optically isotropic liquid crystal phase even when cooled to room temperature.

[Example 5-5]
The cell in which the polymer/liquid crystal composite material PSBP-B2 obtained in Example 5-4 was sandwiched was set in the optical system shown in FIG. 2, and electro-optical properties were measured. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) was used as the light source. The cell was set in the optical system so that The relationship between applied voltage and transmittance was investigated at room temperature. When a rectangular wave of 59.5 V was applied, the transmittance became 88.9% and the transmitted light intensity was saturated. The contrast showed a very high value of 1656.

[Example 6-1]
A liquid crystal composition NLC-C was prepared by mixing the liquid crystal compounds shown in the figure below in the following proportions.

This liquid crystal composition NLC-C had a phase transition temperature (° C.) of N 79.9 I and an average refractive index <n> of 1.60.

The compound (K101) (4.2% by weight) obtained in Example 1 was completely dissolved in the liquid crystal composition NLC-C (95.8% by weight) by heating and stirring at 100°C for 2 minutes to obtain a liquid crystal composition. The product CLC-C1 was obtained.
The phase transition temperature (° C.) of this liquid crystal composition CLC-C1 was N ^* 75.9I. The liquid crystal composition CLC-C1 had a helical pitch of 0.29 μm and a VHR of 99.1%. As a result, it was found that the composition CLC-C1 exhibited a high voltage holding ratio.

[Example 6-2]
Preparation of monomer / liquid crystal mixture Liquid crystal composition NLC-C (92.9% by weight), compound (K101) obtained in Example 1 (0.9% by weight), compound (MC2-04) at 5.90 A liquid crystal composition MLC-C1 was prepared by mixing 0.3% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator.

[Example 6-3]
Preparation of polymer/liquid crystal composite material The liquid crystal composition MLC-C1 was sandwiched between two glass substrates provided with transparent conductive film electrodes that were not subjected to alignment treatment (cell thickness: 10 μm). The cell is heated until the MLC-04 is in the isotropic phase. In this state, ultraviolet light (ultraviolet light intensity of 18 mWcm ⁻² (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer/liquid crystal composite material PDLC-C1 thus obtained maintained the chiral nematic phase even when cooled to room temperature.

[Example 6-4]
The cell in which the polymer/liquid crystal composite material PDLC-C1 obtained in Example 6-3 was sandwiched was set in an optical system, and electro-optical characteristics were measured. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) was used as a light source, and the optical system was set so that the incident angle to the cell was perpendicular to the cell surface. The relationship between applied voltage and transmittance was investigated at room temperature. It was confirmed that the polymer/liquid crystal composite material PDLC-C1 was driven in the normal mode when a voltage of 20 V was applied. When a voltage of 10 V was applied between the electrodes of the polymer/liquid crystal composite material PDLC-C1, the transmitted light intensity was 96.9%, and when a voltage of 22 V was applied, the transmitted light intensity was 10.0%. A liquid crystal device was obtained which was driven and had a high contrast.

[Example 7-1]
The compound (K102) (4.2% by weight) obtained in Example 2 was completely dissolved in the liquid crystal composition NLC-C (95.8% by weight) by heating and stirring at 100°C for 3 minutes to obtain a liquid crystal composition. The product CLC-C2 was obtained.
The phase transition temperature (° C.) of this liquid crystal composition CLC-C2 was N ^* 82.5I. The liquid crystal composition CLC-C2 had a helical pitch of 0.33 μm and a VHR of 99.2%. As a result, it was found that the composition CLC-C2 exhibited a high voltage holding ratio.

[Example 7-2]
Preparation of monomer / liquid crystal mixture Liquid crystal composition NLC-C (92.9% by weight), compound (K102) obtained in Example 2 (0.9% by weight), compound (MC2-04) at 5.90 A liquid crystal composition MLC-C2 was prepared by mixing 0.3% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator.

[Example 7-3]
Preparation of polymer/liquid crystal composite material The liquid crystal composition MLC-C2 was sandwiched between two glass substrates provided with transparent conductive film electrodes that were not subjected to alignment treatment (cell thickness: 10 μm). The cell is heated until the MLC-04 is in the isotropic phase. In this state, ultraviolet light (ultraviolet light intensity of 18 mWcm ⁻² (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer/liquid crystal composite material PDLC-C2 thus obtained maintained the chiral nematic phase even when cooled to room temperature.

[Example 7-4]
The cell in which the polymer/liquid crystal composite material PDLC-C2 obtained in Example 7-3 was sandwiched was set in an optical system, and electro-optical characteristics were measured. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) was used as a light source, and the optical system was set so that the incident angle to the cell was perpendicular to the cell surface. The relationship between applied voltage and transmittance was investigated at room temperature. It was confirmed that when a voltage of 20 V was applied, the polymer/liquid crystal composite material PDLC-C2 was driven in the normal mode. When a voltage of 10 V was applied between the electrodes of the polymer/liquid crystal composite material PDLC-C2, the transmitted light intensity was 91.1%, and when a voltage of 18 V was applied, the transmitted light intensity was 10.0%. A liquid crystal device with high contrast was obtained.

[Example 8-1]
The compound (K103) (4.2% by weight) obtained in Example 3 was completely dissolved in the liquid crystal composition NLC-C (95.8% by weight) by heating and stirring at 100°C for 2 minutes to obtain a liquid crystal composition. The product CLC-C3 was obtained.
The phase transition temperature (° C.) of this liquid crystal composition CLC-C3 was N ^* 75.4I. The liquid crystal composition CLC-C3 had a helical pitch of 0.31 μm and a VHR of 98.0%. As a result, it was found that the composition CLC-C3 exhibited a high voltage holding ratio.

[Example 8-2]
Preparation of monomer / liquid crystal mixture Liquid crystal composition NLC-C (92.9% by weight), compound (K103) obtained in Example 3 (0.9% by weight), compound (MC2-04) at 5.90 A liquid crystal composition MLC-C3 was prepared by mixing 0.3% by weight of 2,2′-dimethoxyphenylacetophenone as a photopolymerization initiator.

[Example 8-3]
Preparation of polymer/liquid crystal composite material The liquid crystal composition MLC-C3 was sandwiched between two glass substrates provided with transparent conductive film electrodes that were not subjected to alignment treatment (cell thickness: 10 μm). The cell is heated until the MLC-04 is in the isotropic phase. In this state, ultraviolet light (ultraviolet light intensity of 18 mWcm ⁻² (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
The polymer/liquid crystal composite material PDLC-C3 thus obtained maintained the chiral nematic phase even when cooled to room temperature.

[Example 8-4]
The cell in which the polymer/liquid crystal composite material PDLC-C3 obtained in Example 8-3 was sandwiched was set in an optical system, and electro-optical characteristics were measured. A white light source of a polarizing microscope (Nikon Eclipse LV100POL) was used as a light source, and the cell was set in the optical system so that the incident angle to the cell was perpendicular to the cell surface. The relationship between applied voltage and transmittance was investigated at room temperature. It was confirmed that the polymer/liquid crystal composite material PDLC-C3 was driven in the normal mode when a voltage of 20 V was applied. When a voltage of 10 V was applied between the electrodes of the polymer/liquid crystal composite material PDLC-C3, the transmitted light intensity was 91.0%, and when a voltage of 20 V was applied, the transmitted light intensity was 10.0%. A liquid crystal device with high contrast was obtained.

Applications of the present invention include, for example, a liquid crystal element such as a display element using a polymer/liquid crystal composite material, or a light control glass.

1 electrode 1
2 electrode 2
3 light source 4 polarizer (polarizer)
5 Comb-shaped electrode cell 6 Analyzer (polarizing plate) (Analyzer)
7 Photodetector

Claims (19)

containing at least one chiral compound represented by the formula (K1) as the chiral component (K) and at least one achiral compound represented by the formula (1-A) or (1-B) as the achiral component (T) A liquid crystal composition containing

(In formula (K1),
Each R ^k1 is independently fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O— provided that no two consecutive —CH ₂ — are replaced by —O—, and in these groups at least one hydrogen may be replaced by a halogen;
each Y ^k1 is independently a single bond or -(CH ₂ ) _n -, where n is an integer from 1 to 20;
nk1 and nk2 are each independently an integer of 0 to 4;
Rod ^k1 is the partial structural formula (Rod1),
In the partial structural formula (Rod1),
R ^k2 is hydrogen, fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms , and in these groups, at least one hydrogen may be replaced with halogen. often;
Ring A ^k1 , Ring A ^k2 and Ring A ^k3 are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ^k1 , Z ^k2 and Z ^k3 are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF ₂ CF ₂ -, -CF=CF-, or -C≡C-;
mk1 and mk2 are each independently an integer of 0 or 1;
In partial structures (X1) and (X2) in which 0 to 4 R ^k1 are linked to the ring structure shown below, 0 to 4 hydrogens among the hydrogens forming the ring structure are replaced with R ^k1 . may be )

(In formulas (1-A) and (1-B),
R ¹¹ and R ¹² are each independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one - CH ₂ — may be replaced by —O—, but two consecutive —CH ₂ — may not be replaced by —O—, and in these groups at least one hydrogen may be replaced by halogen. often;
Ring A ¹¹ , ring A ¹² and ring A ¹³ are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, _-OCF2- , -C
H=CH-, -CF=CF-, or -C≡C-;
X ¹¹ is fluorine, chlorine, -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 CHFCF3} , _-CHFCF2CF3 , -( _CF2 ) _{4 -} F, -( _CF2 ) ₅ -F, _-OCHF2 , _-OCF3 , _{-OCF2CH2F , -OCF2CHF2 ,} -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 ¹¹ and L ¹² are each independently hydrogen or fluorine;
L ¹³ and L ¹⁴ are each independently hydrogen, fluorine, chlorine, or —C≡N, but not both L ¹³ and L ¹⁴ are hydrogen;
S ¹¹ is hydrogen or methyl;
m and n are each independently 0 or 1; ) 2. The liquid crystal composition according to claim 1, wherein the chiral compound represented by formula (K1) is a chiral compound represented by formula (K1-1).

(In formula (K1-1),
Each R ^k1 is independently fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, wherein at least one —CH ₂ — is —O may be replaced by -, but no two consecutive -CH ₂ - are replaced by -O-, and in these groups at least one hydrogen may be replaced by halogen;
nk1 and nk2 are each independently an integer of 0 to 4;
Rod ^k1 is a partial structural formula (Rod1-1) or (Rod1-2),
In the partial structural formulas (Rod1-1) and (Rod1-2),
R ^k2 is hydrogen, fluorine, chlorine, —C≡N, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms , in which at least one hydrogen is replaced by halogen well;
Ring A ^k1 , Ring A ^k2 and Ring A ^k3 are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, 1,3 -dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ^k2 and Z ^k3 are each independently a single bond, -CH ₂ CH ₂ -, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ - , -CH=CH-, -CF ₂ CF ₂ -, -CF=CF-, or -C≡C-;
mk1 and mk2 are each independently an integer of 0 or 1;
Further, in the partial structures (X1) and (X2) in which R ^k1 is linked to the ring structure shown below,
Of the hydrogens forming the ring structure, 0 to 4 hydrogens may be replaced with ^Rk1 . )

In formula (K1-1),
Each R ^k1 is independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with —O—, no two consecutive —CH ₂ — are replaced by —O— and in these groups at least one hydrogen may be replaced by halogen;
nk1 and nk2 are each independently an integer of 0 to 4;
3. The liquid crystal composition according to claim 2, wherein Rod ^k1 is any one of partial structural formulas (Rod1-1A) to (Rod1-1H) and (Rod1-2A) to (Rod1-2H) shown below.

(In the partial structural formulas (Rod1-1A) ~ (Rod1-1H) and (Rod1-2A) ~ (Rod1-2H),
R ^k2 is hydrogen, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms , in which at least one hydrogen may be replaced by halogen;
Further, the partial structure (X3) in which (F) is linked to 1,4-phenylene shown below represents 1,4-phenylene in which one or two hydrogen atoms may be replaced with fluorine. )

Any one of claims 1 to 3, wherein the achiral compound represented by formula (1-A) is any one of the achiral compounds represented by formulas (1-A-01) to (1-A-22). 1. The liquid crystal composition according to item 1.

In formulas (1-A-01) to (1-A-22),
R ¹¹ is independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced with —O—, without two consecutive —CH ₂ — being replaced by —O—;
Ring A ¹¹ and Ring A ¹² are independently 1,4-cyclohexylene, or tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
X ¹¹ is independently fluorine, chlorine, —CF ₃ , or —OCF ₃ ;
(F) is hydrogen or fluorine. Any one of claims 1 to 3, wherein the achiral compound represented by formula (1-B) is any one of the achiral compounds represented by formulas (1-B-01) to (1-B-22). 1. The liquid crystal composition according to item 1.

In formulas (1-B-01) to (1-B-22),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced with —O—. good, but without replacing two consecutive —CH ₂ — with —O—;
Ring A ¹¹ and Ring A ¹² are independently 1,4-cyclohexylene, or tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl;
(F) is hydrogen or fluorine. 6. The liquid crystal composition according to any one of claims 1 to 5, wherein the content of the chiral component (K) in the liquid crystal composition is 0.1 to 30% by weight. 7. The liquid crystal according to any one of claims 1 to 6, wherein the content of the compound represented by formula (1-A) or (1-B) in the achiral component (T) is 50 to 100% by weight. Composition. 7. The compound according to any one of claims 1 to 6, wherein the content of the compound represented by formula (1-A) in the achiral component (T) is 50 to 100% by weight and exhibits an optically isotropic liquid crystal phase. The liquid crystal composition according to the item. 9. The liquid crystal composition according to any one of claims 1 to 8, wherein the chiral component (K) further contains at least one chiral compound represented by formulas (K2) to (K8).

(In formulas (K2) to (K8), R ^K is each independently hydrogen, halogen, —C≡N, —N═C═O, —N═C═S, or alkyl having 1 to 20 carbon atoms. and at least one —CH ₂ — in the alkyl is replaced with —O—, —S—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— at least one hydrogen in the alkyl may be replaced with a halogen;
Each A ^K is independently an aromatic 6- to 8-membered ring, a non-aromatic 3- to 8-membered ring, or a condensed ring having 9 to 20 carbon atoms, and at least one hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, -CH ₂ - in the ring may be replaced by -O-, -S- or -NH-, and -CH= is -N = may be replaced;
Y ^K each independently represents 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 , is a condensed ring having 9 to 20 carbon atoms, at least one hydrogen of these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or haloalkyl, and —CH ₂ — is —O—, —S optionally replaced by - or -NH- and -CH= optionally replaced by -N=;
Each Z ^K is independently a single bond or an alkylene having 1 to 8 carbon atoms, and at least one —CH ₂ — is —O—, —S—, —COO—, —OCO—, —CSO— , -OCS-, -N=N-, -CH=N-, -N=CH-, -CH=CH-, -CF=CF- or -C≡C-, and at least one hydrogen may be replaced by halogen;
each X ^K is independently a single bond, -COO-, -OCO- _, -CH ₂ O-, -OCH 2 -, -CF ₂ O-, -OCF ₂ -, or -CH ₂ CH ₂ -; ;
Each mK is independently an integer of 1-4. ) A monomer/liquid crystal mixture comprising a liquid crystal composition according to any one of claims 1 to 9 and a polymerizable monomer. 11. The monomer/liquid crystal mixture according to claim 10, which exhibits a chiral nematic phase in a temperature range of at least 1° C. or more between -20° C. and 70° C. and has a helical pitch of 700 nm or less in at least part of this temperature range. 11. The monomer/liquid crystal mixture according to claim 10, wherein the liquid crystal composition is a liquid crystal composition having an optically isotropic liquid crystal phase. A monomer/liquid crystal mixture according to any one of claims 10 to 12, wherein the content of polymerizable monomers is in the range of 0.1 to 50% by weight relative to the total amount of the monomer/liquid crystal mixture. Used in a liquid crystal device driven by an optically isotropic liquid crystal phase obtained by polymerizing the monomer/liquid crystal mixture according to claim 10 in a non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase , polymer/liquid crystal composites. A polymer/liquid crystal composite material obtained by polymerizing the monomer/liquid crystal mixture according to claim 10 and used for a light-scattering liquid crystal device driven by a chiral nematic phase. A liquid crystal element comprising a pair of substrates having electrodes, a light control layer sandwiched between the pair of substrates, and an electric field applying means for applying an electric field to the light control layer via the electrodes. There is
16. A liquid crystal device, wherein at least one of the pair of substrates is transparent, and the light control layer is composed of the polymer/liquid crystal composite material according to claim 14 or 15. 17. The liquid crystal device according to claim 16, wherein said polymer/liquid crystal composite material exhibits a chiral nematic phase and constitutes a light scattering liquid crystal device. 18. The liquid crystal device according to claim 16, wherein the content of the polymer in the polymer/liquid crystal composite material is in the range of 0.1 to 50% by weight. A chiral compound represented by the following formula (K101), (K102), or (K103).

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