JP2007039414A - Axially asymmetric optically active cyclohexane compound, liquid crystal composition, liquid crystal display element and formed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically anisotropic compound having polymerizability, polymerization rate of a polymer, polymerization degree, transparency of the polymer, mechanical strength, applicability, solubility, crystallinity, shrinking degree, water permeability, water absorbance, gas permeability, melting point, glass transition point, clear point, heat-resistance, chemical resistance, etc., and its composition, polymer and a formed article containing the polymer. <P>SOLUTION: The compound is expressed by formula (1). The compound, composition, polymer and formed article of the polymer are usable as a polarizing plate, optical compensation plate, luminance improving film, oriented film, color filter, hologram element, liquid crystal display element, adhesive, synthetic polymer having mechanical anisotropy, cosmetics, ornamental articles, anticounterfeit device, non-linear optical element, optical memory element, etc. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an axially asymmetric cyclohexane compound, and specifically to a 2,2′-biphenyl = cyclohexanedicarboxylate compound.
The present invention also relates to a composition containing the compound. The present invention relates to a molded article that can be produced by polymerizing the composition, such as a liquid crystal optical element. Furthermore, this invention relates to the compound used as an intermediate body of a pharmaceutical composition or an agrochemical composition.

  Optical anisotropy for polarizing plates, optical compensators such as N-type c-plates, alignment films, color filters, adhesives, synthetic polymers with mechanical anisotropy, cosmetics, ornaments, anti-counterfeiting devices, etc. The formed body is used. In recent years, liquid crystalline compounds having polymerizability have been used for such molded articles [Japanese Patent Laid-Open Nos. 7-17910 (Patent Document 1), 8-3111 (Patent Document 2), and 9-316032 gazette (patent document 3) etc.]. This liquid crystalline compound having polymerizability has optical anisotropy in a liquid crystal state, and the optical anisotropy is fixed by polymerization. Optical properties required for molded articles with optical anisotropy vary depending on the purpose. When optimizing compounds, in addition to optical anisotropy, polymerizability, physical and chemical properties of the polymer, etc. Is also required. Specifically, the polymerization rate, degree of polymerization, transparency of the polymer, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability , Melting point, glass transition point, clearing point, heat resistance, chemical resistance and the like.

The non-polymerizable liquid crystal composition is used, for example, in a liquid crystal layer portion of a liquid crystal display element driven by an electric field. Such a non-polymerizable liquid crystal composition is prepared by mixing a large number of compounds.
When a non-polymerizable liquid crystal composition is used in an element, it needs to exhibit a spiral structure in the element depending on the type of the element. This helical structure is induced by adding a compound having predetermined characteristics such as optical activity to the liquid crystal composition, and the pitch (p) of the helical structure is determined by adding the optically active compound (concentration c) and the helical induction force (concentration c). Depends on Helical Twisting Power (HTP) (p = HTP ⁻¹ × c ⁻¹ ). The liquid crystal composition having a spiral structure can be used for various applications (devices), such as a PC (Phase Change) display device, a guest / host display device, a TN display device, an STN display device, and an SSCT (Surface Stabilized Cholesteric). It can be used for a texture display element, a PSCT (Polymer Stabilized Cholesteric Texture) display element, and the like.

In addition, compounds having optical activity are highly versatile as constituents of optically active pharmaceuticals or their raw materials, and research on their production methods is continuing.
JP-A-7-17910 JP-A-8-3111 JP-A-9-316032

Under the above conditions, in addition to optical anisotropy, polymerizability, polymer polymerization rate, polymerization degree, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, There is a need for a polymer having optical anisotropy having water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance, etc., or a molded body containing the polymer.
In addition, polarizing plates, optical compensators, alignment films, color filters, holographic elements, liquid crystal display elements, adhesives, synthetic polymers with mechanical anisotropy, cosmetics, and decorative articles containing polymers having optical illegality There is a need for anti-counterfeiting devices, nonlinear optical elements, and optical storage elements.

  When an optically active compound is added to the liquid crystal composition, the amount of the optically active compound added is minimized so that other physical properties such as viscosity, compatibility, and specific resistance value of the liquid crystal composition are not adversely affected. It is necessary to. In general, since optically active compounds usually have low solubility in liquid crystal compositions, it is difficult to increase the amount of optically active compounds added. Therefore, in order to enable the liquid crystal composition to exhibit a helical structure even with a small addition amount, there is a demand for an optically active compound having a large HTP and excellent solubility in other liquid crystal compounds. There is also a need for liquid crystal compositions and liquid crystal display devices containing such compounds.

  The present inventors have found that, for example, 2,2′-biphenyl = cyclohexanedicarboxylate of the present invention has a large HTP and excellent compatibility with other compounds, and the present invention is based on this finding. Was completed.

[1] A compound represented by formula (1).

[In the formula (1), Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a group represented by the formula (T1) or (T2), or hydrogen;
-Z- (AZ) _r- Y- ^Ra (T1)
-Z- (AZ) _r- ^Rb (T2)
{Wherein (T1) and Formula (T2), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
(In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons)
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and any —CH ₂ in these alkyls, alkenyls and alkynyls. -May be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen, alkyl of 1 to 5 carbons, or alkyl halide of 1 to 5 carbons;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-; and r is an integer of 0-5. }]
[1-1] The compound according to [1], wherein in formula (1), at least one of Q ¹ , Q ² , Q ³ and Q ⁴ is a group represented by formula (T1) or (T2) [2] A is independently 1,4-cyclohexylene, or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, Any —CH═ may be replaced by —N═, and in these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
(In formulas (P2) to (P6), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons). The compound according to [1].
[3] A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single bond or a _{-O (CH 2) -, -} O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, - O (CH 2) 10 - a and;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and any —CH ₂ in these alkyls, alkenyls and alkynyls. -May be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN; and r is 0-3 The compound according to [1].
[4] The compound according to any one of [1] to [3], which has optical activity.

[5] A compound represented by formula (1α).
[In the formula (1α), Q ¹ and Q ² are each independently a group represented by the formula (T1) or (T2);
-Z- (AZ) _r- Y- ^Ra (T1)
-Z- (AZ) _r- ^Rb (T2)

{Wherein (T1) and Formula (T2), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
(In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons)
R ^b is hydrogen, halogen, —CN, or alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkynyl having 2 to 10 carbons, and any —CH in these alkyls, alkenyls, and alkynyls. ₂ -may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N =, and in these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms, alkyl halide having 1 to 5 carbon atoms;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-; and r is an integer of 0-5. }]
[6] A is independently 1,4-cyclohexylene, or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, Any —CH═ may be replaced by —N═, and in these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
The compound as described in [5] which is either group represented by these.
[7] A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, or -O _{(CH 2) 10} - a and ;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkynyl having 2 to 10 carbons, and in these alkyls, alkenyls and alkynyls, any —CH _2- may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN; and r is 0-3 The compound according to [5], wherein
[8] The compound according to any one of [5] to [7], which has optical activity.

[9] A compound represented by any one of formulas (1α-1) to (1α-8).
Wherein (1α-1) ~ formula (1α-8), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
{In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkynyl having 2 to 10 carbons, and any —CH in these alkyls, alkenyls and alkynyls ₂ -may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen, alkyl of 1 to 5 carbons, or alkyl halide of 1 to 5 carbons;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-. ]
[10] A is independently 1,4-cyclohexylene or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, Any —CH═ may be replaced by —N═, and in these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
The compound according to [9], which is any one of groups represented by:
[11] A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, or -O _{(CH 2) 10} - a and ;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In the formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl); and R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkynyl having 2 to 10 carbons, or alkoxy having 1 to 10 carbons, and these alkyls, The compound according to [9], wherein any hydrogen in alkenyl and alkynyl may be replaced by halogen or CN.
[12] A compound represented by the formula (1α-2), (1α-3), (1α-4), (1α-6), (1α-7) or (1α-8).
[In the formulas (1α-2), (1α-3), (1α-4), (1α-6), (1α-7) and (1α-8),
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 7 carbons, alkenyl having 2 to 6 carbons, alkynyl having 2 to 6 carbons, or alkoxy having 1 to 7 carbons;
A is independently 1,4-phenylene;
Z may independently be replaced with a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—, in which any hydrogen may be replaced with a halogen; and Y is independently a single bond, or alkylene having 1 to 7 carbons, alkenylene having 2 to 7 carbons, or alkynylene having 2 to 7 carbons, and in these alkylenes, any hydrogen in this alkylene is halogen. Any —CH ₂ — may be replaced by —O—. ]
[13] The compound according to any one of [9] to [12], which has optical activity.

[14] 3 to 90% by weight of a compound selected from the compounds according to any one of [1] to [13], and the formula (M1) or (M2)
^{R c -X a - (A a} -Z a) s -A a -X a -P 1 (M1)
^{P 1 -X a - (A a} -Z a) s -A a -X a -P 1 (M2)
[In Formulas (M1) and (M2), P ¹ is any one of groups represented by Formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons. }
R ^c is hydrogen, fluorine, chlorine, —CN, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, and any — in these alkyls, alkenyls and alkynyls. CH ₂ — may be replaced with —O—, —COO—, or —OCO—, and in these alkyls, alkenyls and alkynyls any hydrogen may be replaced with a halogen;
A ^a is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6. -Diyl, or fluorene-2,7-diyl, but any hydrogen may be replaced by halogen, alkyl having 1 to 3 carbon atoms, or alkyl halide having 1 to 3 carbon atoms;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-;
Z ^a is independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ COO—, —COOCH ₂ CH ₂ —, —CH═CHCOO—, or —OCOCH═CH—; and s is independently from 0 to 3 It is an integer. ]
A composition containing 10 to 97% by weight of at least one compound selected from the compounds represented by:

[15] The composition according to [14], wherein the formula (M1) comprises a compound represented by the formula (M1a), (M1b) or (M1c).
[In formulas (M1a), (M1b) and (M1c), P ¹ is independently any one of the groups represented by formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
R ^c is hydrogen, fluorine, chlorine, —CN, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, and any — in these alkyls, alkenyls and alkynyls. CH ₂ — may be replaced with —O—, —COO—, or —OCO—, and in these alkyls, alkenyls and alkynyls any hydrogen may be replaced with a halogen;
A ^b is independently 1,4-cyclohexylene, or 1,4-phenylene;
W ² is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or alkyl halide having 1 to 3 carbons;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-;
p and q are independently 0 or 1; and m is an integer from 0 to 5. ]
[16] The composition according to [14] or [15], wherein the formula (M2) comprises a compound represented by the formula (M2a), (M2b) or (M2c).
[In formulas (M2a), (M2b) and (M2c), P ¹ is independently any one of groups represented by formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
A ^b is independently 1,4-cyclohexylene, or 1,4-phenylene;
W ² is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or alkyl halide having 1 to 3 carbons;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-; and m is an integer of 0-5. ]

[17] 0.1 to 20% by weight of a compound selected from the compounds according to any one of [1] to [13], and formula (M3)
^{R d - (A c -Z b} ) n-R d (M3)
[In the formula (M3), R ^d is hydrogen, halogen, —C≡C—CN, —CN, alkyl having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons. Any —CH ₂ — may be replaced by —O—, —S—, —CO—, —CF═CF—, or —SiH ₂ —, and any hydrogen in these alkylene, alkenylene and alkynylene; May be replaced by halogen;
^Ac is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl, or naphthalene-2,6-diyl, in which any —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. In these rings, any —CH ₂ CH ₂ — may be replaced by —CH═CH—, and in 1,4-phenylene, any —CH═ may be replaced by —N═, Any hydrogen in the ring may be replaced by halogen, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F;
Z ^b is independently a single bond, alkylene having 1 to 4 carbons, alkenylene having 2 to 4 carbons, or alkynylene having 2 to 4 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. — May be replaced by —O—, —S—, —CF═CF—, —CO—, or —SiH ₂ —, in which any hydrogen may be replaced with a halogen; and n is 2, 3 or 4. ]
A composition containing 80 to 99.9% by weight of at least one compound selected from the compounds represented by:

[18] At least one compound selected from the compounds represented by formula (M3) is represented by formula (2), (3) or (4):
[In Formula (2), Formula (3) and Formula (4), R ¹ is independently alkyl having 1 to 10 carbons, alkenylene having 2 to 10 carbons, or alkynylene having 2 to 10 carbons. In these alkylenes, alkenylenes and alkynylenes, any —CH ₂ — may be replaced with —O—, and in these alkylenes, alkenylenes and alkynylenes, any hydrogen may be replaced with fluorine;
X ¹ is independently fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring B and Ring D are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring E is 1,4-cyclohexylene or 1,4-phenylene, in which any hydrogen may be replaced by fluorine;
Z ⁴ and Z ⁵ are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, or a single bond And L ¹ and L ² are independently hydrogen or fluorine. "
[17] The composition according to [17].
[19] At least one compound selected from the compounds represented by formula (M3) is represented by formula (5) or (6):
[In the formulas (5) and (6), R ² and R ³ are independently alkyl having 1 to 10 carbons, alkenylene having 2 to 10 carbons, or alkynylene having 2 to 10 carbons, In alkylene, alkenylene and alkynylene, any —CH ₂ — may be replaced by —O—, and in these alkylene, alkenylene and alkynylene, any hydrogen may be replaced by fluorine;
X ² is —CN or —C≡C—CN;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring K is 1,4-cyclohexylene or 1,4-phenylene;
Z ⁶ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond;
L ³ , L ⁴ and L ⁵ are independently hydrogen or fluorine; and b, c and d are independently 0 or 1. ]
[17] The composition according to [17].

[20] At least one compound selected from the compounds represented by formula (M3) is represented by formula (7), formula (8), formula (9), formula (10), or formula (11).
[In Formula (7), Formula (8), Formula (9), Formula (10), and Formula (11), R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons, and 2 to 10 carbons. Or an alkenylene having 2 to 10 carbon atoms, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — may be replaced by —O—, and any hydrogen in these alkylene, alkenylene and alkynylene May be replaced by fluorine;
Ring M and Ring P are independently 1,4-cyclohexylene, 1,4-phenylene, or decahydro-2,6-naphthalene;
Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, —COO—, or a single bond; and L ⁶ and L ⁷ are independently hydrogen or fluorine, but L ⁶ and L ⁷ At least one of is fluorine. ]
[17] The composition according to [17].
[21] At least one compound selected from the compounds represented by formula (M3) is represented by formula (12), formula (13), or formula (14):
[In Formula (12), Formula (13), and Formula (14), R ⁶ and R ⁷ are each independently an alkenylene having 1 to 10 carbons, 2 to 10 carbons, or an alkynylene having 2 to 10 carbons. , and the these alkylene, arbitrary -CH 2 - in alkenylene and alkynylene _- may be replaced by -O-, these alkylene, arbitrary hydrogen alkenylene and alkynylene may be replaced by fluorine;
Ring Q, Ring T and Ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. ]
[17] The composition according to [17].

[22] The composition according to any one of [14] to [21], which is a liquid crystal composition.
[23] The composition according to any one of [14] to [21], which is a non-polymerizable liquid crystal composition.
[24] A polymer obtained by polymerizing the composition according to any one of [14] to [22].
[25] The polymer according to [24], which has a weight average molecular weight of 2,000 to 1,000,000.
[26] The polymer according to [24], which has a weight average molecular weight of 2,000 to 500,000.

[27] A molded article having optical anisotropy obtained by orienting the composition according to any one of [14] to [23] and then fixing the orientation of the liquid crystal by irradiation with electromagnetic waves.
[28] The molded article according to [27], wherein the fixed liquid crystal orientation is twist orientation.
[29] An optical element comprising the molded article according to [27] or [28].
[30] The optical element according to [29], which exhibits circular dichroism in a visible light region that selectively reflects light in a part or all of a wavelength of 350 to 750 nm.
[31] The optical element according to [29] or [30], which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm.
[32] The composition according to any one of [17] to [21], the polymer according to any one of [24] to [26], the molded article according to [27] or [28], or [29] A liquid crystal display device comprising the optical device according to any one of [31]. -

In this specification, in order to show both acrylic acid and methacrylic acid, it may be described as “(meth) acrylic acid”.
In the present specification, “alkyl” is a linear or branched alkyl group, and examples thereof include methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl and the like. “Alkenyl” includes a straight or branched alkenyl group having 1 to 3 double bonds, and specifically includes ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl. 2-butenyl, 3-butenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2 -Heptenyl, 1-octenyl, 2-octenyl, 1,3-octadienyl, 2-nonenyl, 1,3-nonadienyl, 2-decenyl and the like. “Alkynyl” includes linear or branched alkynyl groups having 1 to 3 triple bonds, specifically, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl. , 3-butynyl, 1-pentynyl, 2-pentynyl, 4-pentynyl, 1-octynyl, 6-methyl-1-heptynyl, 2-decynyl and the like.

  In the present specification, “alkylene” is a linear or branched alkyl group, for example, linear or branched such as methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and the like. And an alkylene group. “Alkenylene” is a linear or branched alkenylene group, and examples thereof include vinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, and 3-pentenylene. “Alkynylene” is a linear or branched alkynylene group, and examples thereof include ethynylene, propynylene, 1-butynylene, 2-butynylene, 1-pentynylene, 2-pentynylene, and 3-pentynylene.

In the present specification, the liquid crystal compound is a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. In this specification, a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be simply referred to as a compound, a composition, and an element, respectively.
In the present specification, the compound represented by the formula (1) may be referred to as “compound (1)”, “compound of the formula (1)” or the like.

The meaning of “arbitrary —CH ₂ — may be replaced by —O—, —CH═CH—, etc.” is shown as an example. A part of groups in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— is C ₃ H ₇ O—, CH ₃ O (CH ₂ ) ₂ —, CH _{3. OCH 2 O-, H 2 C =} CH (CH 2) 3 -, CH 3 CH = CH (CH 2) 2 -, and _CH 3 _CH = CHCH ₂ is O-. Thus, the “arbitrary” means “at least one selected without distinction”. In consideration of the chemical stability of the compound, a group in which oxygen and oxygen are not adjacent to each other is preferable to a group in which oxygen and oxygen are adjacent. Therefore, for example, CH ₃ OCH ₂ O— in which oxygen and oxygen are not adjacent to each other is more preferable than CH ₃ OOCH ₂ — in which oxygen and oxygen are adjacent.

The compound according to a preferred embodiment of the present invention and the composition containing this compound can exhibit a good liquid crystal phase temperature range and orientation.
The compound according to a preferred embodiment of the present invention and a composition containing this compound are well soluble in other liquid crystal compounds and are difficult to crystallize at low temperatures in the liquid crystal composition, so that the usable temperature range (nematic phase temperature range) Can be spread.
In addition to the optical anisotropy, the compound according to a preferred embodiment of the present invention and the composition containing the compound include, for example, polymerizability, polymer polymerization rate, polymerization degree, polymer transparency, and mechanical strength. Optics with favorable physical and chemical properties such as coating properties, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance A polymer having anisotropy or a molded body containing the polymer can be provided.
The compound according to a preferred embodiment of the present invention and the composition containing this compound are compositions containing a polymerizable liquid crystal compound that can be polymerized by irradiation with electromagnetic waves.
A compound according to a preferred embodiment of the present invention and a composition containing the compound are a polarizing plate, an optical compensator, an alignment film, a color filter, a holographic element, a liquid crystal display element, and an adhesive containing a polymer having optical anisotropy. Synthetic polymers having mechanical anisotropy, cosmetics, decorations, anti-counterfeiting devices, nonlinear optical elements, and optical memory elements can be provided.

According to a preferred embodiment of the present invention, an optically active compound having a large HTP and excellent solubility in other liquid crystal compounds, and a liquid crystal composition and a liquid crystal display device containing such a compound can be provided.
Moreover, according to the preferable aspect of this invention, the composition etc. which have a wide liquid crystal phase temperature range and a moderate spiral pitch, and can be used for a liquid crystal display element can be provided.

  Moreover, according to the preferable aspect of this invention, the structural component of a highly versatile optically active pharmaceutical or its raw material can be provided.

1. Compound of the Present Invention The compound of the present invention is 2,2′-biphenyl = cyclohexanedicarboxylate represented by the above formula (1). In formula (1), Q ¹ , Q ² , Q ³ and Q ⁴ are independently a group represented by the above formula (T1) or (T2), or hydrogen. Preferably, Q ¹ and Q ² are a group represented by the formula (T1) or (T2), and Q ³ and Q ⁴ are hydrogen [compound represented by the formula (1α)] .

R ^a in Formula (T1) is any polymerizable group represented by Formulas (P1) to (P8), and in Formulas (P1) to (P8), W is independently hydrogen, halogen, C1-C3 alkyl or C1-C3 haloalkyl. Preferably, in formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons, and more preferably independently. , Hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl. In addition, when it has the distinction of the steric configuration of W, it may be a mixture of cis and trans, or each may be independent.
When R ^a is a polymerizable group represented by formulas (P1) to (P4), R ^a is suitable for cationic polymerization. On the other hand, when R ^a is a polymerizable group represented by formulas (P5) to (P8), R ^a is suitable for radical polymerization. At this time, the polymerization can be carried out more rapidly by adding a polymerization initiator or raising the reaction temperature.

R ^b in Formula (T1) is hydrogen, halogen, —CN, or alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkynyl having 2 to 10 carbons, and these alkyl, alkenyl, and alkynyl Any —CH ₂ — may be replaced by —O—, —S—, or —CO—, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN. Preferably, R ^b is fluorine, chlorine, —CN, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, fluoroalkyl having 1 to 10 carbons, or 1 carbon. -10 fluoroalkoxy.

A in the formulas (T1) and (T2) is a divalent group having a ring structure. Specifically, A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6-diyl. In the rings, any —CH ₂ — may be replaced by —O—, and in these rings, any —CH═ may be replaced by —N═, and in these rings, any hydrogen is a halogen, It may be substituted with alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms.
Preferably, A has the following structure:
More preferably, A is 1,4-cyclohexylene, 1,4-phenylene, and 1,4-phenylene in which any hydrogen in the group is replaced by fluorine, chlorine, methyl or trifluoromethyl. Most preferably, A has the following structure:

  In A in the formulas (T1) and (T2), when they have a steric configuration distinction such as cyclohexylene, they may be a mixture of cis and trans, or each may be independent. Even if each element of the compound according to the first aspect of the present invention contains more isotope elements than naturally occurring, there is no significant difference in physical properties.

Z in the formulas (T1) and (T2) is a linking group. Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, and in this alkylene, any hydrogen may be replaced by a halogen. Particularly preferably, Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ .
Z represents a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O—. , —O (CH ₂ ) ₃ —, —CH═CH—, —CH═CHCH ₂ CH ₂ —, —CH ₂ CH ₂ CH═CH—, —CH═CHCH ₂ O—, —OCH ₂ CH═CH— , —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO— or —OCOCH═CH— is preferred because the compound (1) of the present invention tends to improve liquid crystallinity. Z is a bond group containing a fluorine, for example, _{-CF 2 CF 2 -, - CF} 2 O -, - OCF 2 -, - CH 2 CH 2 CF 2 O -, - OCF 2 CH 2 CH 2 - is the is present The compound of the first aspect of the invention is preferred because it tends to decrease the optical anisotropy or increase the dielectric anisotropy. When Z is a linking group containing a triple bond, such as —C≡C—, —C≡CCOO—, or —OCOC≡C—, there is a tendency to induce large optical anisotropy in the compound (1) of the present invention. .

Y in formula (T1) is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, Any —CH ₂ — may be replaced by —O—, —S—, —COO—, or —OCO—. When Y contains an asymmetric carbon, it may be a racemate or an optically active substance.

  R in the formula (T1) is an integer of 0 to 5, and preferably an integer of 0 to 3.

  The group represented by the formula (T1) or (T2) can be suitably used in any of the above structures, but is preferably a group represented by the following formulas (1-a) to (1-m).

-Z-R ^e (1-a)
-Z-Ph-R ^e (1-b)
-Z-Ch-R ^e (1-c)
-Z-Ph-Z-Ph-R ^e (1-d)
-Z-Ch-Z-Ph-R ^e (1-e)
-Z-Ph-Z-Ch-R ^e (1-f)
-Z-Ch-Z-Ch-R ^e (1-g)
-Z-Ph-Z-Ph-Z-Ph-R ^e (1-h)
-Z-Ch-Z-Ph-Z-Ph-R ^e (1-i)
-Z-Ph-Z-Ch-Z-Ph-R ^e (1-j)
-Z-Ph-Z-Ph-Z-Ch-R ^e (1-k)
-Z-Ch-Z-Ch-Z-Ph-R ^e (1-l)
-Z-Ph-Z-Ch-Z-Ch-R ^e (1-m)
[In the formulas (1-a) to (1-m), Ph is 1,4-phenylene which may be substituted, Ch is 1,4-cyclohexylene which may be substituted, and Z and Y are the same as above. Indicating meaning, R ^e represents Y—R ^a or R ^b . ]

  Of the groups represented by the above formulas (1-a) to (1-m), particularly preferred are groups represented by (1-b), (1-d) and (1-h).

2. Production method of the compound of the present invention The compound (1) of the present invention is prepared by Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, Organic Synthesis (John & Wily & Sons, Inc.) , Organic Reactions (John & Wily & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), etc. Specifically, the compound (1) of the present invention can be produced by bonding an organic residue containing a 6-membered ring or a condensed ring structure. Here, the condensed ring refers to a product in which two or more rings are condensed. For example, the condensed ring includes a six-membered ring structure such as naphthalene.
Hereinafter, based on the synthesis example of compound (1A)-(1S) which is a specific aspect of the compound (1) of this invention, the manufacturing method of the compound (1) of this invention is shown. In these synthesis examples, MG ¹ and MG ² are organic residues containing one or more 6-membered rings or condensed rings, and may be different or the same.

[Compounds (1A) to (1J)]
Compounds (1A) to (1J) can be synthesized by the scheme shown below.
Compound (1A) in which Z is a single bond can be synthesized by a cross-coupling reaction of boronic acid (i1) and bromide (i2) (Scheme 1).
In addition, by dehydrating condensation reaction between the carboxylic acid (i3) and the compound (i4) having a hydroxyl group, the compound (1B) in which the bonding group is —COO— is obtained, and the carbonyl group is fluorinated with a fluorine anion. A compound (1C) in which the bonding group is —CF ₂ O— can be synthesized (Scheme 2).
From bromide (i5), compound (i4) and base (B ⁻ ), compound (1D) having —CH ₂ O— in the bonding group can be synthesized (Scheme 3). Also, PPh ₃ is allowed to act on bromide (i5) to synthesize a phosphonium salt (i6), and aldehyde (i7) is allowed to act on ylide obtained from the phosphonium salt (i6) and a base to carry out a Wittig reaction. A compound (1E) in which the group is —CH═CH— can be synthesized (Scheme 3). Compound (1F) in which the linking group is —CH ₂ CH ₂ — can be synthesized by reducing compound (1E) (Scheme 3).
By fluorination with fluorine anion diketone (i8), binding group is _-CF 2 CF ₂ - can be synthesized in a compound (1G) (Scheme 4). At this time, since the reaction proceeds in two steps, the compound (i9) whose bonding group is —CF ₂ CO— can be taken out by adjusting the titer of the fluorine anion (Scheme 4).
By sequentially acting tetrafluoroethylene and (i11) on the lithiated product (i10), a compound (1H) in which the bonding group is —CF═CF— can be synthesized (Scheme 5).
A compound (1J) in which the bonding group is —C≡C— can be synthesized by a cross-coupling coupling reaction between alkyne (i12) and bromide (i2) in the presence of a transition metal catalyst.

[Compounds (1K) to (1P)]
Compounds (1K) to (1P) can be synthesized by the scheme shown below.
Carboxylic acid (i14) is synthesized by Wittig reaction of aldehyde (i13), and compound (1K) in which the bonding group is —CH═CHCOO— is obtained by dehydration condensation reaction of carboxylic acid (i14) and compound (i4). Can be synthesized (Scheme 7). In addition, the compound (1L) in which the bonding group is —CH ₂ CH ₂ COO— can be synthesized by reducing the compound (1K), and further the carbonyl group of the compound (1L) is fluorinated with a fluorine anion to form a bonding group. A compound (1M) in which is —CH ₂ CH ₂ CF ₂ O— can be synthesized.
A compound (1N) in which the bonding group is —C≡CCOO— can be synthesized by a dehydration condensation reaction between the carboxylic acid (i15) synthesized by lithiation of the alkyne (i12) and the action of CO ₂ and the compound (i4). (Scheme 8). Furthermore, by fluorinating the compound (1N) carbonyl group with a fluorine anion, the compound (1P) in which the bonding group is —C≡CCF ₂ O— can be synthesized.

[Compounds (1Q) to (1S)]
Compounds (1Q) to (1S) can be synthesized by the scheme shown below.
Compound (1Q) having a — (CH ₂ ) ₃ O— group can be synthesized from bromide (i16), compound (i4) and a base (Scheme 9). In addition, a bonding group is converted to — (CH ₂ ) by reacting ylide obtained from phosphonium salt (i17) synthesized by allowing PPh ₃ to act on bromide (i16) and a base to cause aldehyde (i7) to act on Wittig reaction. A compound (1R) in which ₂ CH═CH— can be synthesized (Scheme 9). In addition, the compound (1S) in which the bonding group is — (CH ₂ ) ₄ — can be synthesized by reducing the compound (1R) (Scheme 9).
Compound (1T) having a —CH═CHCH ₂ O— group can be synthesized from chloride (i18), compound (i4) and a base (Scheme 10).

Furthermore, a specific compound of 2,2′-biphenyl = cyclohexanedicarboxylate of the compound (1) can be synthesized by appropriately combining using the above method and the like.
For example, a dehydration condensation reaction between 1,2-cyclohexyldicarboxylic acid and 2,2′-biphenol optionally having a substituent, 1,2-cyclohexanedicarboxylic anhydride and the 2,2′-biphenol The compound (1) can also be synthesized by a two-stage esterification reaction such as a ring-opening condensation reaction and a dehydration condensation reaction.
Further, after esterification by 1,2-cyclohexyldicarboxylic acid and 2-halogenated phenol which may have a substituent by dehydration condensation, 2,2′-biphenyl is obtained by cyclization reaction by dehalogenation or the like. = Can also be induced in the construction of cyclohexanedicarboxylate moieties.

Among the compounds (1) that can be synthesized by the above method, specific examples of preferred compounds are compounds represented by the following formulas (1-1) to (1-8). However, A, Z, Y, R ^a and R ^b have the same meaning as described in the item [1], and a plurality of A, Z, Y, R ^a and R ^b may be the same as or different from each other.

In formulas (1-1) to (1-8), a preferable structure of A is the following structure. In the following ring structure, there is no distinction between the right and left of the bonding position, and any may be used.

In formulas (1-1) to (1-8), preferred Z is a single bond, —COO—, or —CH ₂ O—.
In the formula (1-1) to (1-8), Y is preferably a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O ( CH ₂ ) ₄ —, —O (CH ₂ ) ₅ —, —O (CH ₂ ) ₆ —, —O (CH ₂ ) ₇ —, —O (CH ₂ ) ₈ —, —O (CH ₂ ) ₉ — Or —O (CH ₂ ) ₁₀ —.
In formulas (1-1) to (1-8), preferred R ^a is (P2), (P3) or (P5).
In formulas (1-1) to (1-8), preferable R ^b is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , alkyl having 1 to 7 carbons, or alkyl having 1 to 7 carbons. Alkoxy.

  Of the compounds (1-1) to (1-8), the compound (1-2), (1-3), (1-5) or (1-6) is particularly preferable. The cyclohexane carboxyl moiety of the compound (1) may be a cis isomer or a trans isomer as long as it shows the required characteristics. However, when (T1) and (T2) are the same and the cyclohexane carboxyl moiety is a cis form, the compound (1) is a meso form and becomes non-optically active. The biphenyl skeleton is said to have a stable structure in which the dihedral angle of two benzene rings is about 45 °. From this point, the cyclohexane carboxyl moiety is preferably a trans isomer.

  The spiral direction of the compound (1) and the composition of the present invention containing the compound (1) may be any, and the circularly polarized light separating element produced from the compound has left circular polarization or right circular polarization according to the direction of the spiral. Selective reflection.

3. Composition of the Invention The composition of the present invention is a composition containing two or more compounds, wherein at least one compound is the compound (1) of the present invention.
When the composition of the present invention is a liquid crystal composition, the composition preferably contains at least one compound (1) and a polymerizable liquid crystal or a non-polymerizable liquid crystal composition.

The polymerizable liquid crystal contained in the composition of the present invention is preferably at least one polymerizable compound selected from the formulas (M1) and (M2).
^{R b -X a - (A a} -Z a) s-A a -X a -P 1 (M1)
^{P 1 -X a - (A a} -Z a) s-A a -X a -P 1 (M2)
[In Formulas (M1) and (M2), P ¹ is independently selected from Formulas (P9) to (P12).
W is hydrogen, halogen, alkyl having 1 to 3 carbons or fluoroalkyl; R ^b is independently hydrogen, fluorine, chlorine, —CN or 1 carbon. An alkyl of ˜20 in which any —CH ₂ — may be replaced with —O—, —COO—, or —OCO—, and any hydrogen may be replaced with halogen; A ^a is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6. - diyl or 2,7-but diyl, arbitrary hydrogen halogen, alkyl of 1 to 3 carbon atoms, or may be replaced by an alkyl halide of 1 to 3 carbon atoms,; X ^a DE To a single bond or alkylene having 1 to 20 carbon atoms, arbitrary _-CH 2 - in the alkylene may, -O -, - COO- or -OCO- may be replaced by; Z ^a is independently Single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — _{OCF 2 -, -, - CH} 2 CH 2 COO -, - COOCH 2 CH 2 -, - CH = CHCOO-, or -OCOCH = CH- and is; s is independently an integer of 1 to 3. ]

  Preferred compounds represented by the formulas (M1) and (M2) are the compounds (M1a) to (M2c). In the composition of the present invention, the preferable content of the compounds (M1a) to (M2c) is 10 to 99% by weight, more preferably 10 to 97% by weight, and still more preferably 50 to 95% by weight. is there.

As the non-polymerizable liquid crystal contained in the composition of the present invention, at least one polymerizable compound selected from the formula (M3) is preferable.
^{R c - (A c -Z b} ) n-R c (M3)
[In the formula (M3), R ^c is independently hydrogen, alkyl having 1 to 20 carbons, halogen, —C≡C—CN, or —CN, and in this alkyl, any —CH ₂ — is -O -, - S -, - CO -, - CH = CH -, - CF = CF -, - C≡C-, or -SiH ₂ - may be replaced by, and any hydrogen substituted with halogen It is at best; A ^c are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4 - a tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, any _-CH 2 _- in these rings - is, -O -, - S -, - CO-, or -SiH ₂ - may be replaced by, any of -CH ₂ H ₂ - may be replaced by -CH = CH-, = any -CH in 1,4-phenylene may be replaced by -N =, and any hydrogen in these rings halogen, - CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F may be substituted; Z ^b is independently a single bond or alkylene having 1 to 4 carbon atoms. In this alkylene, any —CH ₂ — is replaced by —O—, —S—, —CH═CH—, —CF═CF—, —C≡C—, —CO—, or —SiH ₂ —. And any hydrogen may be replaced by halogen; and n is 2, 3 or 4. ]

  Preferred compounds represented by formula (M3) are compounds (2) to (14). Moreover, in the composition of this invention, preferable content of compound (2)-(14) is 0.1 to 20 weight%, More preferably, it is 0.1 to 5 weight%.

  For the purpose of improving physical properties, a polymerization initiator, a solvent, a surfactant, an antioxidant, a filler, an ultraviolet absorber, a sensitizer and the like may be added to the composition of the present invention. The chemical structure and composition of the additive are not limited. When the composition is a liquid crystal composition, the content of each component is such that the liquid crystal properties of the liquid crystal composition are not impaired. Specific examples of known liquid crystal compounds that are non-polymerizable are disclosed in the database LiqCryst (registered trademark, LCI Publisher, Hamburg, Germany) and publications thereof.

In order to optimize the characteristics of the composition, an optically active compound other than the compound (1) may be added. Preferred examples of the optically active compound are the formulas (OP-1) to (OP-24). In these formulas, Ak represents alkyl and alkoxy having 1 to 15 carbon atoms, and Me, Et, and Ph represent methyl, ethyl, and phenyl, respectively. The polymerizable group P ² may have any structure as long as it exhibits polymerizability, but the group shown below is particularly preferable. t is an integer of 2-8.

  In order to facilitate handling during use of the composition of the present invention or to prevent polymerization during storage, a stabilizer may be added to the composition of the present invention. Any known stabilizer can be used, for example, 4-ethoxyphenol, hydroquinone, 3,5-di-t-butyl-4-hydroxytoluene (BHT), and the like.

  The composition of the present invention can be dissolved in a solvent and applied to a substrate or the like. Solvents include hexane, heptane, toluene, xylene, methoxybenzene, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone. , Cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, chloroform, dichloromethane, dichloroethane, t-butyl alcohol, diacetone alcohol, butyl cellosolve Examples thereof include a single solvent or a plurality of mixed solvents.

  The composition of the present invention is a thin film formed by a method such as spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire barcode, dip coating, spray coating, meniscus coating or casting film forming method. It can be spread and applied to a substrate or the like by removing the solvent.

  By orienting the surface of the substrate before coating, the composition of the present invention can be oriented on the substrate. For example, a thin film made of polyimide, polyamide, polyvinyl alcohol, or the like is formed, and this is rubbed with a rayon cloth or the like, silicon oxide is obliquely vapor-deposited, stretched film, photo-alignment film, This is a rubbing-free orientation using an ion beam or the like. As another processing method, there is a rubbing treatment of the substrate directly with a rayon cloth or the like. In some cases, the substrate surface may not be processed.

  The orientation of the composition can be fixed by irradiation with electromagnetic waves. At this time, the wavelength of the electromagnetic wave is preferably 300 nm or more, particularly around 365 nm. The temperature at the time of irradiation is a temperature at which the composition is in a liquid crystal state, but is preferably 100 ° C. or lower in order to prevent thermal polymerization.

  The composition of the present invention containing an optically active compound exhibits a helical structure on the coated substrate. If the composition is polymerized, a molded body having twist orientation can be produced. For example, the composition of the present invention has a circularly polarized light separating function in light having a wavelength (λ) that satisfies the formula “λ = refractive index × spiral pitch”. Such a composition can be used as a brightness enhancement film. In the composition of the present invention, the spiral direction and pitch can be optimized by appropriately selecting the type and addition amount of the optically active compound.

  The molded article of the present invention can be produced by applying the composition of the present invention on a substrate to form a coating film, and fixing the nematic alignment formed by the composition in a liquid crystal state by light irradiation. Examples of the substrate include triacetylcellulose, diacetylcellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, and polycarbonate. Specific product names include “Arton” from JSR Corporation, “Zeonex” and “Zeonor” from Nippon Zeon Corporation, “Appel” from Mitsui Chemicals, Inc. The substrate may be a uniaxially stretched film or a biaxially stretched film. The substrate may be subjected to surface treatment such as saponification treatment, corona treatment, or plasma treatment in advance.

  The thickness of the molded product of the present invention varies depending on the required characteristics and the optical anisotropy value of the molded product. Preferably it is 0.05-50 micrometers, More preferably, it is 0.1-20 micrometers, More preferably, it is 0.5-5 micrometers. A preferable retardation value is 0.05 to 50 μm, more preferably 0.1 to 20 μm, and further preferably 0.5 to 10 μm. The haze value of the molded body is 1.5% or less, more preferably 1.0% or less. The transmittance of the molded body in the visible light region is 80% or more, more preferably 85% or more. In order to obtain sufficient polarization performance, a haze value of 1.5% or less is preferable. A transmittance of 80% or more is a preferable condition for maintaining the brightness when the molded body is used for a liquid crystal display element.

4). Polymer of the Present Invention The polymer of the present invention is a polymer that can be produced by radical polymerization or cationic polymerization of a composition containing the compound (1) of the present invention. This polymer is preferably a copolymer having a helical structure.

  The composition obtained by mixing the compound (1) and the nematic liquid crystal composition exhibits a cholesteric phase. A fixed cholesteric phase (twisted orientation) can be obtained by forming a thin film of this composition by coating on a substrate and irradiating it with light to polymerize it. This can be used for anti-counterfeiting of reflection type polarizing plates, color filters, ornaments, ID cards, etc., nonlinear optical elements, optical storage devices, and the like. In addition, a broadband reflective polarizer can be manufactured by tilting the pitch in a direction perpendicular to the substrate. The pitch ramp can be produced using techniques known to those skilled in the art.

  The polymerization for producing the polymer of the present invention can be carried out by irradiating energy such as electromagnetic waves. The irradiated electromagnetic waves are, for example, ultraviolet rays, infrared rays, visible rays, X-rays, and γ rays. In addition, high energy particles such as ions and electrons may be irradiated. Polymerization can be performed in air, but the polymerization time can be shortened by irradiating light in an inert gas such as nitrogen or argon.

  In the polymer of the present invention, a polymerizable compound having no liquid crystallinity may be added for the purpose of adjusting mechanical strength, thermal strength, coatability, orientation and the like. The compound to be added is preferably a (meth) acrylate compound, a vinyl compound, a styrene compound, a vinyl ether compound, an oxirane compound, or an oxetane compound. Multifunctional acrylates, vinyl ethers, oxiranes, and oxetanes may be added to further increase the mechanical and thermal strength of the polymer.

  In the polymer of the present invention, a surfactant may be added to facilitate application to a substrate or the like or to control the alignment of liquid crystals. The addition amount of the surfactant varies depending on the type and purpose of the surfactant, but is 0.01 to 5% by weight, more preferably 0.01 to 1% by weight with respect to the liquid crystal composition of the present invention. .

  Examples of the photoradical polymerization initiator used in the production of the polymer of the present invention are 1173 and 4265 from Darocur series of Ciba Specialty, and 184, 369, 500, 651, 784, 819 from Irgacure series. 907, 1300, 1700, 1800, 1850, 2959, etc., but any known one can be used.

  Other examples of the photoradical polymerization initiator used in the production of the polymer of the present invention include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl. -1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy 2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / p-dimethylaminobenzoate Methyl acid mixture, benzophenone / methyltriethanol Although Min mixture, etc., can be used any of those known.

  Examples of the photocationic polymerization initiator used in the production of the polymer of the present invention include UCC Corporation's Syracure UVI-6990 and 6974, Asahi Denka Co., Ltd. Adekaoptomer SP-150, 152, 170 and 172, Photoinitiator 2074 of Rhodia Co., Ltd., Irgacure 250 of Ciba Specialty Co., Ltd., DTS-102 of Midori Chemical Co., Ltd., etc., but any known one can be used.

The polymer of the present invention having thermoplasticity can be used for adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorations, anti-counterfeiting devices, nonlinear optical materials, information storage materials, and the like. These are linear polymers having few branched structures, and are obtained from a composition mainly composed of a monofunctional compound. These weight average molecular weights are 5 * 10 < ² > -1 * 10 < ⁶ >, Preferably it is 2 * 10 < ³ > -5 * 10 < ⁶ >, More preferably, it is 2 * 10 < ³ > -5 * 10 < ⁵ >.

5. Optical element and liquid crystal display element of the present invention The optical element of the present invention is an element including the molded article of the present invention. Examples of the optical element of the present invention include thermosetting resins for polarizing plates for liquid crystal display elements, optical compensation plates, brightness enhancement films, negative c-plates, and the like. The thermosetting resin is a polymer having a network structure, and can be obtained as a polymer having a high degree of polymerization by polymerizing a composition mainly composed of a bifunctional compound. These polymers are difficult to dissolve in solvents and have high hardness. The molecular weight of these polymers is difficult to measure and difficult to define, but is preferably close to infinity.

Moreover, the liquid crystal display element of this invention is a liquid crystal display element containing the polymer, molded object, or optical element of this invention. Moreover, the liquid crystal display element of this invention is a liquid crystal display element which used the composition adjusted with the nonpolymerizable liquid crystal composition containing a compound (1) as a component.
The composition used for the liquid crystal display element of the present invention is prepared by the method described above. In the above-described method, for example, the compounds contained in the composition can be mixed and dissolved by heating to adjust.

  A compound having a high clearing point or a low minimum temperature of the liquid crystal phase contributes to a wide temperature range of the nematic phase in the composition. Preferred compositions have low viscosity and optical anisotropy suitable for the device mode. The large dielectric anisotropy of the compound contributes to the low threshold voltage of the composition. With such a composition, an element having characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a small driving voltage, a small power consumption, and a large voltage holding ratio can be obtained. .

Furthermore, you may adjust the physical property of a composition by adding a suitable additive to the said composition. Additives well known to those skilled in the art include, for example, dichroic dyes such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. A composition for a device may be prepared. Compound (1) may be added as a chiral dopant to induce the helical structure of the liquid crystal to give the necessary twist angle.
A preferred pitch for TN elements and TN-TFT elements is in the range of 40-200 μm. A preferred pitch for STN elements is in the range of 6-20 μm. A preferred pitch for the BTN device is in the range of 1.5-4 μm. It is preferable to add a relatively large amount of chiral dopant to the composition for a PC element. A compound other than the compound of the present invention may be added for the purpose of adjusting the temperature dependence of the pitch. Preferred examples of this additive are the above-mentioned optically active compounds (Op-1) to (Op-12).

6). In addition, the compound of the present invention was developed as an optically active compound mainly contained in a composition used for a liquid crystal display device, but as an intermediate for pharmaceutical compounds, agricultural chemical compounds, dye compounds having a similar skeleton. Is also useful.

Hereinafter, the present invention will be described in detail by way of examples. In Examples, the phase transition temperature was measured with a melting point measuring apparatus equipped with a polarizing microscope and DSC, and the chemical structure of the synthesized compound was confirmed with ¹ H-NMR and ¹³ C-NMR. C, N, Ch, and I represent a crystal, a nematic phase, a cholesteric phase, and an isotropic liquid, respectively. HTP calculated the helical induction force of the cholesteric liquid crystal composition obtained by mixing the compound (1) with the mother liquid crystal ZLI-1132 from the formula [p = HTP ⁻¹ × c ⁻¹ ]. Here, c is% by weight of the compound (1), and p is pitch (μm). The p was determined from the gap between the obtained Grandjean line and the angle between the two glass plates of the wedge cell after injecting and leaving the cholesteric liquid crystal composition in a Cano wedge cell.

(1S, 2S)-(+)-(1-5-1, R ^b = H)

Under a nitrogen atmosphere, trans-1,2-cyclohexanedicarboxylic acid was optically resolved by a conventional method using (S)-(−)-α-methylbenzylamine or the like (1S, 2S)-(+)-(ex1- 1) 8.9 g (52 mmol), 9.5 g (51 mmol) of (ex1-2) and 18.4 g (151 mmol) of 4-dimethylaminopyridine (DMAP) were added to 200 ml of methylene chloride, and the mixture was stirred on an ice bath (Scheme 1). ). A solution of 21.0 g (102 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 50 ml of methylene chloride was added dropwise, followed by stirring at room temperature for 6 days. Insoluble matter was filtered off, and the filtrate was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain the desired product (1S, 2S)-(+)-(1-5-1, R ^b = H) 2. 3 g (7 mmol) was synthesized (in Table 9, 1-5-1 R ^b = H compound). The melting point of the synthesized compound was 169.2 to 170.4 ° C.

Synthesis of (1S, 2S)-(+)-(1-5-1, R ^b = Br) Y. Kubo et al., Tetrahedron Letters, 40, 6019 (1999) instead of (ex1-2) in Example 1 The synthesis was carried out under the same conditions as in Example 1 except that 17.5 g (51 mmol) of 5,5′-dibromo-1,1′-bi-2-phenol synthesized by the method described above was used. , (1S, 2S)-(+)-(1-5-1, R ^b = Br)
3.8 g (8 mmol) (compound of 1-5-1 R ^b = Br in Table 9).

Synthesis of (1S, 2S)-(+)-(1-5-6, R ^b = H)
4.8 g (10 mmol) of (1S, 2S)-(+)-(1-5-1, R ^b = Br) synthesized in Example 2, 1.4 g (2 mmol) of Pd (PPh ₃ ) ₂ Cl ₂ Then, 0.4 g (2 mmol) of CuI was added to 100 ml of triethylamine and stirred at room temperature under a nitrogen atmosphere. Subsequently, 5.6 g (50 mmol) of trimethylsilylacetylene was dropped, and the mixture was stirred at 70 ° C. for 48 hours. After stirring, the insoluble material was filtered off, water was added, and the mixture was extracted with methylene chloride. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. 100 ml of methanol and 4.1 g (30 mmol) of potassium carbonate were added and stirred at room temperature for 30 minutes. Water was added and extracted with methylene chloride. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and recrystallization to obtain 3.0 g (8 mmol) of (1S, 2S)-(+)-(1-5-6, R ^b = H).

Synthesis of (1S, 2S)-(+)-(1-6-18, R ^b = C ₃ H ₇ )
Under a nitrogen atmosphere, 3.0 g (8 mmol) of (1S, 2S)-(+)-(1-5-6, R ^b = H) synthesized in Example 3 and 5.9 g of 4-propyliodobenzene ( 24 mmol), 1.1 g (1 mmol) of Pd (PPh ₃ ) ₄ and 0.2 g (1 mmol) of CuI were added to 100 ml of triethylamine and stirred at room temperature for 3 hours. Insoluble material was filtered off, water was added, and the mixture was extracted with methylene chloride. Water was added and extracted with methylene chloride. After extraction by washing with water, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and recrystallization to synthesize 3.6 g (6 mmol) of the title (1S, 2S)-(+)-(1-6-18, R ^b = C ₃ H ₇ ). (In Table 11, 1-6-18 R ^b = C ₃ H ₇ compound)

According to the methods of Examples 1 to 4, the compounds (1-1-1) to (1-8-30) described in Tables 1 to 16, which are specific compounds of the compound (1), are synthesized. . These compounds are shown in Tables 1-16. In the table, two A ^{1 to} A ³ , Z ^{1 to} Z ³ , Y ¹ , R ^a and R ^b in the structural formula are the same, and the abbreviations in ^Ra and the structure are shown below.
The conformation of each compound described in Tables 1 to 16 may be any. Moreover, the black circle in the structure of a ring and a coupling group in the formula of Tables 1-16 shows the coupling | bond part with an adjacent group. In the formulas in Tables 1 to 16, when Z is a single bond, the description may be omitted. In the table, a blank in Z ¹ indicates a single bond.

  The compound, composition, polymer, and molded product using the polymer of the present invention are a polarizing plate, an optical compensator, a brightness enhancement film, an alignment film, a color filter, a holographic element, a liquid crystal display element, an adhesive, a mechanical The present invention can be applied to synthetic polymers having anisotropy, cosmetics, decorations, anti-counterfeiting devices, nonlinear optical elements, optical storage elements, and the like.

Claims (32)

The compound represented by Formula (1).

[In the formula (1), Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a group represented by the formula (T1) or (T2), or hydrogen;
-Z- (AZ) _r- Y- ^Ra (T1)
-Z- (AZ) _r- ^Rb (T2)

{Wherein (T1) and Formula (T2), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
(In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons)
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and any —CH ₂ in these alkyls, alkenyls and alkynyls. -May be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen, alkyl of 1 to 5 carbons, or alkyl halide of 1 to 5 carbons;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-; and r is an integer of 0-5. }]
A is independently 1,4-cyclohexylene, or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, and any — CH = may be replaced by -N =, and in these rings any hydrogen may be replaced by halogen, alkyl of 1 to 5 carbon atoms or alkyl halide of 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
(In formulas (P2) to (P6), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons.)
The compound of Claim 1 which is either group represented by these. A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, or -O _{(CH 2) 10} - a and ;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
A group represented by:
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and any —CH ₂ in these alkyls, alkenyls and alkynyls. -May be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN; and r is 0-3 The compound of claim 1, wherein The compound according to any one of claims 1 to 3, which has optical activity.
A compound represented by formula (1α).
[In the formula (1α), Q ¹ and Q ² are each independently a group represented by the formula (T1) or (T2);
-Z- (AZ) _r- Y- ^Ra (T1)
-Z- (AZ) _r- ^Rb (T2)

{Wherein (T1) and Formula (T2), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
(In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons)
R ^b is hydrogen, halogen, —CN, or alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkynyl having 2 to 10 carbons, and any —CH in these alkyls, alkenyls, and alkynyls. ₂ -may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N =, and in these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms, alkyl halide having 1 to 5 carbon atoms;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-; and r is an integer of 0-5. }] A is independently 1,4-cyclohexylene, or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, and any — CH = may be replaced by -N =, and in these rings any hydrogen may be replaced by halogen, alkyl of 1 to 5 carbon atoms or alkyl halide of 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
The compound of Claim 5 which is either group represented by these. A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, or -O _{(CH 2) 10} - a and ;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
A group represented by:
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkynyl having 2 to 10 carbons, and in these alkyls, alkenyls and alkynyls, any —CH _2- may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN; and r is 0-3 The compound according to claim 5, wherein   The compound according to claim 5, which has optical activity. A compound represented by any one of formulas (1α-1) to (1α-8).
Wherein (1α-1) ~ formula (1α-8), R ^a is either a polymerizable group represented by the formula (P1) ~ (P8);
{In formulas (P1) to (P8), W is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkynyl having 2 to 10 carbons, and any —CH in these alkyls, alkenyls and alkynyls ₂ -may be replaced by -O-, -S-, or -CO-, and in these alkyls, alkenyls and alkynyls, any hydrogen may be replaced by halogen or CN;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, or fluorene-2,7-diyl, in which any —CH ₂ — may be replaced by —O— -CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen, alkyl of 1 to 5 carbons, or alkyl halide of 1 to 5 carbons;
Z is independently a single bond, or alkylene having 1 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms, and any —CH ₂ in these alkylene, alkenylene, and alkynylene. -May be replaced by -O-, -CO-, -COO-, -OCO-, or -CF = CF-, in which any hydrogen may be replaced by a halogen;
Y is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — May be replaced by -O-, -S-, -COO-, or -OCO-. ]
A is independently 1,4-cyclohexylene, or 1,4-phenylene, and in these rings, any —CH ₂ — may be replaced by —O—, and any — CH = may be replaced by -N =, and in these rings any hydrogen may be replaced by halogen, alkyl of 1 to 5 carbon atoms or alkyl halide of 1 to 5 carbon atoms;
Z is independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, in this alkylene any hydrogen may be replaced with a halogen;
Y is independently a single bond, alkylene having 1 to 11 carbons, alkenylene having 2 to 12 carbons, or alkynylene having 2 to 12 carbons, and in these alkylene, alkenylene or alkynylene, any —CH ₂ — May be replaced by —O—, —S—, —COO—, or —OCO—; and R ^a is of formula (P2) to (P6)
The compound of Claim 9 which is either group represented by these. A independently has the following structure:
Z is independently a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—;
Y is independently a single _{bond, -O (CH 2) -,} - O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - O (CH 2) _{5 -, - O (CH 2} ) 6 -, - O (CH 2) 7 -, - O (CH 2) 8 -, - O (CH 2) 9 -, or -O _{(CH 2) 10} - a and ;
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
And R ^b is hydrogen, halogen, —CN, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkynyl having 2 to 10 carbons, or 1 to 10 carbons. 10. The compound of claim 9, wherein any hydrogen in these alkyls, alkenyls and alkynyls may be replaced with halogen or CN. A compound represented by the formula (1α-2), (1α-3), (1α-4), (1α-6), (1α-7) or (1α-8).
[In the formulas (1α-2), (1α-3), (1α-4), (1α-6), (1α-7) and (1α-8),
R ^a is the formula (P2), (P3), (P5) or (P6)
(In formulas (P2), (P3), (P5) and (P6), W is independently hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.)
A group represented by:
R ^b is hydrogen, halogen, —CN, alkyl having 1 to 7 carbons, alkenyl having 2 to 6 carbons, alkynyl having 2 to 6 carbons, or alkoxy having 1 to 7 carbons;
A is independently 1,4-phenylene;
Z may independently be replaced with a single bond, —COO—, —OCO—, —OCH ₂ — or —CH ₂ O—, in which any hydrogen may be replaced with a halogen; and Y is independently a single bond, or alkylene having 1 to 7 carbons, alkenylene having 2 to 7 carbons, or alkynylene having 2 to 7 carbons, and in these alkylenes, any hydrogen in this alkylene is halogen. Any —CH ₂ — may be replaced by —O—. ]
  The compound according to any one of claims 9 to 12, which has optical activity. 3 to 90% by weight of a compound selected from the compounds according to any of claims 1 to 13 and the formula (M1) or (M2)

^{R c -X a - (A a} -Z a) s -A a -X a -P 1 (M1)
^{P 1 -X a - (A a} -Z a) s -A a -X a -P 1 (M2)

[In Formulas (M1) and (M2), P ¹ is any one of groups represented by Formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or haloalkyl having 1 to 3 carbons. }
R ^c is hydrogen, fluorine, chlorine, —CN, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, and any — in these alkyls, alkenyls and alkynyls. CH ₂ — may be replaced with —O—, —COO—, or —OCO—, and in these alkyls, alkenyls and alkynyls any hydrogen may be replaced with a halogen;
A ^a is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6. -Diyl, or fluorene-2,7-diyl, but any hydrogen may be replaced by halogen, alkyl having 1 to 3 carbon atoms, or alkyl halide having 1 to 3 carbon atoms;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-;
Z ^a is independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ COO—, —COOCH ₂ CH ₂ —, —CH═CHCOO—, or —OCOCH═CH—; and s is independently from 0 to 3 It is an integer. ]
A composition containing 10 to 97% by weight of at least one compound selected from the compounds represented by: The composition according to claim 14, wherein the formula (M1) comprises a compound represented by the formula (M1a), (M1b) or (M1c).
[In formulas (M1a), (M1b) and (M1c), P ¹ is independently any one of the groups represented by formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
R ^c is hydrogen, fluorine, chlorine, —CN, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, and any — in these alkyls, alkenyls and alkynyls. CH ₂ — may be replaced with —O—, —COO—, or —OCO—, and in these alkyls, alkenyls and alkynyls any hydrogen may be replaced with a halogen;
A ^b is independently 1,4-cyclohexylene, or 1,4-phenylene;
W ² is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or alkyl halide having 1 to 3 carbons;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-;
p and q are independently 0 or 1; and m is an integer from 0 to 5. ] The composition according to claim 14 or 15, wherein the formula (M2) comprises a compound represented by the formula (M2a), (M2b) or (M2c).
[In formulas (M2a), (M2b) and (M2c), P ¹ is independently any one of groups represented by formulas (P9) to (P12);
{In Formulas (P9) to (P12), W ¹ is hydrogen, halogen, alkyl having 1 to 3 carbons, or fluoroalkyl having 1 to 3 carbons. }
A ^b is independently 1,4-cyclohexylene, or 1,4-phenylene;
W ² is independently hydrogen, halogen, alkyl having 1 to 3 carbons, or alkyl halide having 1 to 3 carbons;
X ^a is independently a single bond, alkylene having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. -May be replaced by -O-, -COO-, or -OCO-; and m is an integer of 0-5. ] 0.1 to 20% by weight of a compound selected from the compounds according to any one of claims 1 to 13 and the formula (M3)
^{R d - (A c -Z b} ) n-R d (M3)
[In the formula (M3), R ^d is hydrogen, halogen, —C≡C—CN, —CN, alkyl having 1 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons. Any —CH ₂ — may be replaced by —O—, —S—, —CO—, —CF═CF—, or —SiH ₂ —, and any hydrogen in these alkylene, alkenylene and alkynylene; May be replaced by halogen;
^Ac is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl, or naphthalene-2,6-diyl, in which any —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. In these rings, any —CH ₂ CH ₂ — may be replaced by —CH═CH—, and in 1,4-phenylene, any —CH═ may be replaced by —N═, Any hydrogen in the ring may be replaced by halogen, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F;
Z ^b is independently a single bond, alkylene having 1 to 4 carbons, alkenylene having 2 to 4 carbons, or alkynylene having 2 to 4 carbons, and any —CH ₂ in these alkylene, alkenylene and alkynylene. — May be replaced by —O—, —S—, —CF═CF—, —CO—, or —SiH ₂ —, in which any hydrogen may be replaced with a halogen; and n is 2, 3 or 4. ]
A composition containing 80 to 99.9% by weight of at least one compound selected from the compounds represented by: At least one compound selected from the compounds represented by formula (M3) is represented by formula (2), (3) or (4)
[In Formula (2), Formula (3) and Formula (4), R ¹ is independently alkyl having 1 to 10 carbons, alkenylene having 2 to 10 carbons, or alkynylene having 2 to 10 carbons. In these alkylenes, alkenylenes and alkynylenes, any —CH ₂ — may be replaced with —O—, and in these alkylenes, alkenylenes and alkynylenes, any hydrogen may be replaced with fluorine;
X ¹ is independently fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring B and Ring D are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring E is 1,4-cyclohexylene or 1,4-phenylene, in which any hydrogen may be replaced by fluorine;
Z ⁴ and Z ⁵ are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, or a single bond And L ¹ and L ² are independently hydrogen or fluorine. "
The composition of Claim 17 which is a compound represented by these. At least one compound selected from the compounds represented by formula (M3) is represented by formula (5) or (6):
[In the formulas (5) and (6), R ² and R ³ are independently alkyl having 1 to 10 carbons, alkenylene having 2 to 10 carbons, or alkynylene having 2 to 10 carbons, In alkylene, alkenylene and alkynylene, any —CH ₂ — may be replaced by —O—, and in these alkylene, alkenylene and alkynylene, any hydrogen may be replaced by fluorine;
X ² is —CN or —C≡C—CN;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring K is 1,4-cyclohexylene or 1,4-phenylene;
Z ⁶ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond;
L ³ , L ⁴ and L ⁵ are independently hydrogen or fluorine; and b, c and d are independently 0 or 1. ]
The composition of Claim 17 which is a compound represented by these. At least one compound selected from the compounds represented by formula (M3) is represented by formula (7), formula (8), formula (9), formula (10), or formula (11).
[In Formula (7), Formula (8), Formula (9), Formula (10), and Formula (11), R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons, and 2 to 10 carbons. Or an alkenylene having 2 to 10 carbon atoms, and in these alkylene, alkenylene and alkynylene, any —CH ₂ — may be replaced by —O—, and any hydrogen in these alkylene, alkenylene and alkynylene May be replaced by fluorine;
Ring M and Ring P are independently 1,4-cyclohexylene, 1,4-phenylene, or decahydro-2,6-naphthalene;
Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, —COO—, or a single bond; and L ⁶ and L ⁷ are independently hydrogen or fluorine, but L ⁶ and L ⁷ At least one of is fluorine. ]
The composition of Claim 17 which is a compound represented by these. At least one compound selected from the compounds represented by formula (M3) is represented by formula (12), formula (13), or formula (14).
[In Formula (12), Formula (13), and Formula (14), R ⁶ and R ⁷ are each independently an alkenylene having 1 to 10 carbons, 2 to 10 carbons, or an alkynylene having 2 to 10 carbons. And in these alkylenes, alkenylenes and alkynylenes, any —CH ₂ — may be replaced with —O—, and in these alkylenes, alkenylenes and alkynylenes, any hydrogen may be replaced with fluorine;
Ring Q, Ring T and Ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. ]
The composition of Claim 17 which is a compound represented by these.   The composition according to any one of claims 14 to 21, which is a liquid crystal composition.   The composition according to any one of claims 14 to 21, which is a non-polymerizable liquid crystal composition.   The polymer obtained by superposing | polymerizing the composition in any one of Claims 14-22.   The polymer according to claim 24, having a weight average molecular weight of 2,000 to 1,000,000.   The polymer according to claim 24, having a weight average molecular weight of 2,000 to 500,000.   24. A molded article having optical anisotropy obtained by orienting the composition according to any one of claims 14 to 23 and then fixing the orientation of liquid crystal by irradiation with electromagnetic waves.   The molded body according to claim 27, wherein the orientation of the fixed liquid crystal is twist orientation.   An optical element comprising the molded article according to claim 27 or 28.   30. The optical element according to claim 29, wherein the optical element exhibits circular dichroism in a visible light region that selectively reflects light in a part or all of a wavelength of 350 to 750 nm.   The optical element according to claim 29 or 30, which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm.   The composition according to any one of claims 17 to 21, the polymer according to any one of claims 24 to 26, the molded product according to claim 27 or 28, or any one of claims 29 to 31. A liquid crystal display element comprising the optical element described. -