JP2005281223A - Optically active compound having 1,2-cyclohexylene ring, liquid crystal composition, liquid crystal display element and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition which can control the spiral pitch and uses an optically active compound having a large spiral induction power, a liquid crystal display element using the same, a polymer of a composition comprising such an optically active compound, a polarizing plate using the polymer, an optical compensator such as an N-type c-plate, an oriented membrane, a color filter, an adhesive, a synthetic polymer having a mechanical anisotropy, a cosmetic, a decorative article, a device for preventing forgery and the like. <P>SOLUTION: The optically active compound is represented by formula (1) [wherein Q<SP>1</SP>and Q<SP>2</SP>are each a group represented by formula (T1): -Z-(A-Z)r-Y-R<SP>a</SP>(wherein Z and Y are each a connecting group; A is a cyclic group; R<SP>a</SP>is a polymerizable group; and r is an integer of 1-5) or a group prepresented by formula (T2): -Z-(A-Z)r-R<SP>b</SP>(wherein Z, A, and r are the same as defined above; and R<SP>b</SP>is a monovalent group)]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optically active compound having a 1,2-cyclohexane ring, a liquid crystal composition containing the same, a liquid crystal display element, and a molded article having optical anisotropy that can be produced by polymerizing these liquid crystal compositions.

  In recent years, a polymerizable liquid crystalline compound has been used for a molded article having optical anisotropy (see Patent Documents 1 to 3). These have optical anisotropy in a liquid crystal state, and the optical anisotropy is fixed by polymerization. Since the optical properties required for the molded product vary depending on the purpose, a compound suitable for the purpose is required. Moreover, when optimizing a compound, in addition to the above-mentioned anisotropy, the polymerizability and the physical and chemical characteristics of the polymer must satisfy the requirements. This property includes compound polymerization rate, degree of polymerization, polymer transparency, mechanical strength, coatability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, Clearing point, heat resistance, chemical resistance, etc.

  Moreover, a non-polymerizable liquid crystal composition is used for a liquid crystal display element, and the composition is prepared by mixing many compounds. Therefore, the compound must be miscible with other compounds. In addition, since the device may be used at a temperature below freezing point, a compound having good compatibility at a low temperature is preferable. 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. .

A helical structure is induced by adding an optically active compound to the liquid crystal composition. The pitch (p) depends on the addition amount (concentration c) of the optically active compound and the helical induction power (HTP). p = HTP ⁻¹ × c ⁻¹ . The liquid crystal composition having a spiral structure can be used for various applications. For example, PC (phase change) display element, guest / host display element, TN display element, STN display element, SSCT (Surface Stabilized Cholesteric Texture) display element, PSCT (Polymer Stabilized Cholesteric Texture) display element, N-type c -Plate (negative c-plate).

  In any application, it is appropriate to minimize the amount of the optically active compound added so that other physical properties such as viscosity, compatibility, and specific resistance are not adversely affected. Therefore, an optically active compound having a large HTP is required. Also, optically active compounds usually have low solubility in liquid crystal compositions, and it is difficult to increase the amount of addition, and optically active compounds having a large HTP are required.

  Optical anisotropic when applied to polarizing plates, optical compensators such as N-type c-plates, alignment films, color filters, adhesives, synthetic polymers with mechanical anisotropy, cosmetics, decorations, and anti-counterfeiting devices Utilize molded products that have properties. Polymer degree of polymerization, transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance For example, an excellent molded body is required. Moreover, the liquid crystal composition containing an optically active compound needs to be excellent in the polymerization rate.

JP-A-7-17910 JP-A-8-3111 JP-A-9-316032

  The first object of the present invention is to provide an optically active compound having a large HTP, excellent solubility with other liquid crystal compounds and having a 1,2-cyclohexane ring, and a liquid crystal composition and a liquid crystal display device containing the compound. Is to provide. The second purpose is transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance It is an object of the present invention to provide a polymer excellent in properties such as, and a molded article having optical anisotropy produced from the polymer. The third purpose is a polarizing plate, an optical compensator, an alignment film, a color filter, a holographic element, a liquid crystal display element, an adhesive, a synthetic polymer having mechanical anisotropy, a cosmetic, and a decorative article containing the polymer. An anti-counterfeiting device, a non-linear optical element, and an optical memory element.

  As a result of studying to solve the above problems, the present inventors have found that the optically active compound having a 1,2-cyclohexane ring of the present invention has a large HTP and excellent compatibility with other compounds. In addition, the liquid crystal composition containing the compound of the present invention exhibits a good liquid crystal phase temperature range and a helical alignment, and when the polymerizable compound is contained as a constituent element, it has excellent polymerizability and coatability. The polymer is excellent as an optical compensation thin film such as a reflective polarizing plate, a retardation plate or an N-type c-plate, and a composition with a non-polymerizable liquid crystal has a wide liquid crystal phase temperature range and an appropriate helical pitch, The present invention was completed by finding that it is excellent in liquid crystal display device applications. The present invention includes the following items [1] to [32].

−Ｚ−（Ａ−Ｚ）ｒ−Ｙ−Ｒ^a （Ｔ１）
−Ｚ−（Ａ−Ｚ）ｒ−Ｒ^b （Ｔ２）

[1] An optically active compound represented by the following formula (1).

-Z- (AZ) r-Y- ^Ra (T1)
-Z- (AZ) r- ^Rb (T2)

Here, Q ¹ and Q ² are independently a group represented by the formula (T1) or (T2); R ^a is any of the polymerizable group represented by formula (P1) ~ (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 And in this alkyl any —CH ₂ — may be replaced by —O—, —S—, —CO—, —CH═CH—, or C≡C—, and any hydrogen may be halogen or CN A may independently be 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl. And any in these rings CH 2 _- may be replaced by -O-, arbitrary -CH = may be replaced by -N =, optional hydrogen halogen, alkyl or carbon number of 1 to 5 carbon atoms in these rings 1 to 5 halogenated alkyls may be substituted; Z is independently a single bond or alkylene having 1 to 20 carbon atoms, in which any —CH ₂ — represents —O—, — CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— may be replaced, and any hydrogen may be replaced with a halogen; Independently, it is a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — may be replaced by —O—, —S—, —COO—, or —OCO—. R is 1 It is an integer of ~ 5.

[2] 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═ -N = may be substituted, and in these rings, any hydrogen may be substituted with halogen, alkyl having 1 to 5 carbon atoms, or alkyl halide having 1 to 5 carbon atoms. Active compound.

[3] Z is independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary —CH ₂ — is —O—, —CO—, —COO— or —OCO—. Item 3. The optically active compound according to Item 1 or 2, wherein any hydrogen may be replaced with a halogen.

[4] Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylenes, any —CH ₂ — may be replaced by —O—, —COO—, or —OCO—. The optically active compound according to any one of Items 1 to 3.

[5] The optically active compound according to any one of items 1 to 4, wherein r is 1.

[6] The optically active compound according to any one of items 1 to 4, wherein r is 2.

[7] The optically active compound according to any one of items 1 to 4, wherein r is 3.

[8] The optically active compound according to any one of items 1 to 7, wherein Q ¹ and Q ² are each independently a group represented by the formula (T1).

[9] The optically active compound according to any one of items 1 to 8, wherein R ^a is any one of groups represented by formulas (P2) to (P6).

[10] The optically active compound according to any one of [1] to [9], wherein W is hydrogen, fluorine, chlorine, methyl, ethyl, or trifluoromethyl.

[11] The optically active compound according to any one of items 1 to 7, wherein Q ¹ and Q ² are each independently any one of groups represented by the formula (T2).

[12] R ^b is hydrogen, fluorine, chlorine, —CN or alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — is replaced by —O—, —CO— or —CH═CH—. Item 12. The optically active compound according to any one of Items 1 to 7 and Item 11, wherein any hydrogen may be replaced by -F or -CN.

[13] A liquid crystal composition containing at least two compounds, wherein the at least one compound is the compound according to any one of items 1 to 12.

[14] The compound selected from the compounds described in any one of Items 1 to 12 is 3 to 90% by weight, and the other compounds are selected from the compounds represented by the formulas (M1) and (M2) Item 14. The liquid crystal composition according to item 13, which is a compound containing 10 to 97% by weight of the prepared at least one compound.
^{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)

Here, P ¹ is any of the groups represented by 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, or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, —COO—, or —OCO—. Any hydrogen may be replaced by 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 is halogen, alkyl having 1 to 3 carbons, or carbon Number 1 to 3 halogene It may be replaced by an alkyl; independently X ^a, single bond, or an alkylene having 1 to 20 carbon atoms, arbitrary _-CH 2 - in the alkylene may, -O -, - COO- or Z ^a may independently be 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 is; s is an integer of 1 to 3 independently.

[15] The liquid crystal composition according to item 13 or 14, wherein all of the compounds are polymerizable compounds.
At least one polymerizable compound selected from the compounds represented by formula (M1) or (M2) is represented by formula (M1a), (M1b), (M1c), (M2a), (M2b), or (M2c). Item 15. The liquid crystal composition according to item 14, which is a compound represented by:

Here, P ¹ is independently a group represented by Formulas (P9) to (P12); R ^c is independently hydrogen, fluorine, chlorine, —CN, or alkyl having 1 to 20 carbons. And in this alkyl, any —CH ₂ — may be replaced with —O—, —COO—, or OCO—, and any hydrogen may be replaced with halogen; A ^b independently , 1,4-cyclohexylene to be xylene or 1,4-phenylene,; ^{W 2} is independently halogen, alkyl having 1 to 3 carbon atoms, or a halogenated alkyl having 1 to 3 carbon atoms; X ^a is Independently a single bond, alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—; Independently, 0 or 1 and m is 0-5. Is a number.

[17] A polymer obtained by polymerizing the composition according to any one of items 13 to 16.

[18] The polymer according to item 17, having a weight average molecular weight of 500 to 1,000,000.

[19] The polymer according to item 17, having a weight average molecular weight of 1,000 to 500,000.

[20] A molded article having optical anisotropy obtained by orienting the composition according to any one of items 13 to 16 and then fixing the orientation of the liquid crystal by irradiation with electromagnetic waves.

[21] The shaped article according to item 20, wherein the orientation of the fixed liquid crystal is twist orientation.

[22] An optical element comprising the molded article according to item 20 or 21.

[23] The optical element according to item 22, 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.

[24] The optical element according to item 22, which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm.

[25] A liquid crystal display element comprising at least one selected from the polymer according to items 17 to 19, the molded article according to items 20 and 21, and the optical element according to items 22 to 24.

[26] The liquid crystal composition according to item 13, wherein all of the compounds are non-polymerizable compounds.

[27] 0.1 to 20% by weight of the compound according to any one of items 1 to 7 and 11 to 12, and 80 to 99.9% by weight of the formula (M3) Item 27. A liquid crystal composition according to item 26, comprising at least one compound selected from compounds.
^{R d - (A c -Z b} ) n-R d (M3)

Here, R ^d is hydrogen, halogen, —C≡C—CN, —CN, or alkyl having 1 to 20 carbons, and in this alkyl, arbitrary —CH ₂ — is —O—, —S—, —CO—, —CH═CH—, —CF═CF—, —C≡C—, or SiH ₂ — may be substituted, and any hydrogen may be replaced with a 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 any of —CH ₂ — in these rings may be replaced by —O—, —S—, —CO—, or SiH ₂ —, and any — CH ₂ CH ₂ — is —CH═CH -, And in 1,4-phenylene any —CH═ may be replaced by —N═, and in these rings any hydrogen is 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 an alkylene having 1 to 4 carbon atoms, and in this alkylene, any —CH _2- may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —C≡C—, —CO—, or SiH ₂ —, and any hydrogen may be halogenated And n is 2, 3 or 4.

[28] The liquid crystal composition according to item 27, wherein at least one compound selected from the compounds represented by formula (M3) is a compound represented by formula (2), (3) or (4).

Here, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen May be replaced by 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 And 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 _{) 4 -, - COO -,} - CF 2 O -, - OCF 2 -, - CH = CH-, or a single bond; and ^{L 1} and ^{L 2} are independently hydrogen or fluorine.

[29] The liquid crystal composition according to item 27 or 28, wherein at least one compound selected from compounds represented by formula (M3) is a compound represented by formula (5) or (6).

Here, R ² and R ³ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and X ² may be —CN or —C≡C—CN; Ring G may be 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 Yes; 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 ^{Yes; L} 3, L ⁴ you Fine and L ⁵ are independently hydrogen or fluorine; and b, c and d are independently 0 or 1.

[30] At least one compound selected from the compounds represented by formula (M3) is the compound represented by formula (7), (8), (9), (10) or (11). 30. The liquid crystal composition according to any one of -29.

Here, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH— Hydrogen may be replaced by fluorine and R ⁵ may independently be fluorine; ring M and ring P are independently 1,4-cyclohexylene, 1,4-phenylene or decahydro- 2,6-naphthylene; 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. However, at least one of L ⁶ and L ⁷ is fluorine.

[31] The liquid crystal composition according to any one of items 27 to 30, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13) and (14).

Here, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, And any hydrogen may be replaced by fluorine; ring Q, ring T and ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or any hydrogen is replaced by fluorine. And Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. .

[32] A liquid crystal display device comprising the liquid crystal composition according to any one of items 27 to 31.

  Compound (1) is excellent in solubility with other liquid crystal compounds, has good HTP, and lowers the crystallization temperature of the obtained composition. A composition containing a polymerizable liquid crystal compound as a constituent element can be polymerized by irradiation with electromagnetic waves to obtain a polymer. This polymer has transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition point, clearing point, heat resistance, chemical resistance, etc. Also excellent. In addition, this polymer is 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 synthetic polymer having mechanical anisotropy, a cosmetic, a decorative article, and a counterfeit. It can be used for prevention devices, nonlinear optical elements, optical storage elements, and the like. A composition composed of a non-polymerizable compound has a wide liquid crystal phase temperature range and an appropriate helical pitch, and can be used for a liquid crystal display device.

  The term liquid crystal compound is a generic 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. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be referred to as a compound, a composition, and an element, respectively. A compound represented by the formula (1) or the like may be referred to as a compound (1) or a compound of the formula (1). Acrylate and methacrylate may be referred to as (meth) acrylate.

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 word “arbitrary” means “at least one selected without distinction”. In consideration of the chemical stability of the compound, 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 to each other.

The first of the present invention is an optically active compound having a 1,2-cyclohexane ring represented by the formula (1). Q ¹ and Q ² are independently the formula (T1) or (T2).

R ^a in formulas (T1) and (T2) is ^a polymerizable group represented by formulas (P1) to (P8), and W in the formula is independently hydrogen, halogen, alkyl having 1 to 3 carbon atoms, or It is a C1-C3 fluoroalkyl. Preferred W is hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl.

  The polymerizable groups (P1) to (P4) are suitable for cationic polymerization, and (P5) to (P8) are suitable for radical polymerization. Polymerization can be performed more rapidly by adding a polymerization initiator or raising the reaction temperature.

R ^b in the formulas (T1) and (T2) is hydrogen, halogen, —CN, or alkyl having 1 to 10 carbons, and in this alkyl, any —CH ₂ — is —O—, —S—, — CO—, —CH═CH—, or —C≡C— may be replaced, and any hydrogen may be replaced with halogen or —CN. Preferred R ^b is fluorine, chlorine, —CN, alkyl having 1 to 5 carbons, alkoxy, alkenyl, fluoroalkyl, or fluoroalkoxy.

A in the formulas (T1) and (T2) is a divalent group having a ring structure. These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, in these rings Arbitrary —CH ₂ — may be replaced by —O—, Arbitrary —CH═ may be replaced by —N═, and in these rings, any hydrogen is halogen, alkyl having 1 to 5 carbon atoms. Alternatively, it may be replaced with an alkyl halide having 1 to 5 carbon atoms.

Preferred examples of A are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which any hydrogen in the group is replaced by fluorine, chlorine, methyl or trifluoromethyl. Specific examples are as follows.

In the case of having a configuration distinction such as cyclohexylene, it may be a mixture of cis and trans, or each may be independent. Even if each element of the compound 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, and in this alkylene, any —CH ₂ — represents —O—, —CO—, —COO—, —OCO—, —CH═CH. -, -CF = CF- or -C≡C- may be substituted, and any hydrogen may be replaced by halogen.

Z is 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—, — When CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, or —OCOCH═CH— is preferred, a compound having the same tends to improve liquid crystallinity. _-CF 2 _CF 2 containing fluorine _{-, - CF 2 O -,} - OCF 2 -, - CH 2 CH 2 CF 2 O -, - OCF 2 CH 2 CH 2 - may reduce the optical anisotropy or dielectric This tends to increase the rate anisotropy and is preferred. -C≡C-, -C≡CCOO-, and -OCOC≡C- containing a triple bond tend to induce large optical anisotropy. More preferable Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ .

Y in Formula (1) is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — is —O—, —S—, —COO—, or —OCO—. May be replaced.

Preferred Y is alkylene having 1 to 10 carbons which may be replaced by —O—, —COO— or —OCO in any —CH ₂ —. Further, when it contains an asymmetric carbon, it may be a racemate or an optically active substance.

By appropriately selecting R ^a , A, Z, Y, W, and r, the compound (1) having the desired physical properties can be obtained.

The liquid crystalline residues of the formulas (T1) and (T2) can be suitably used in any structure, but are preferably (1-a) to (1-l). In the following, Ph is 1,4-phenylene which may be substituted, Ch is 1,4-cyclohexylene which may be substituted, Z and Y have the same meaning as described above, and ^Re is Y-R ^a Or ^Rb is shown. .

-Z-Ph-R ^e (1-a)
-Z-Ch-R ^e (1-b)
-Z-Ph-Z-Ph-R ^e (1-c)
-Z-Ch-Z-Ph-R ^e (1-d)
-Z-Ph-Z-Ch-R ^e (1-e)
-Z-Ch-Z-Ch-R ^e (1-f)
-Z-Ph-Z-Ph-Z-Ph-R ^e (1-g)
-Z-Ch-Z-Ph-Z-Ph-R ^e (1-h)
-Z-Ph-Z-Ch-Z-Ph-R ^e (1-i)
-Z-Ph-Z-Ph-Z-Ch-R ^e (1-j)
-Z-Ch-Z-Ch-Z-Ph-R ^e (1-k)
-Z-Ph-Z-Ch-Z-Ch-R ^e (1-l)

  Particularly preferred among (1-a) to (1-l) are (1-a), (1-c) and (1-g).

  Compound (1) dissolves well in other liquid crystal compounds. Since the compound (1) is difficult to crystallize at a low temperature in the liquid crystal composition, the usable temperature range (nematic) can be expanded.

The production method of compound (1) will be described. Compound (1) is 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., can be produced by appropriately combining organic synthetic chemical techniques. Specifically, it can be constructed by combining organic residues containing a 6-membered ring structure. Next, the coupling method will be described. In the following, MG ¹ and MG ² are organic residues containing one or more 6-membered ring structures, and they may be different or the same. (1A) to (1P) are the compound (1).

Compounds (1A) to (1J) can be synthesized by the route shown in Chemical Formula 1. Compound (1A) in which Z is a single bond can be synthesized by a cross-coupling reaction of boronic acid (i1) and bromide (i2). Compound (1B) in which the linking group is —COO— can be synthesized by dehydration condensation reaction of carboxylic acid (i3) and compound (i4) having a hydroxyl group, and further bonded by fluorinating the carbonyl group with a fluorine anion. A compound (1C) in which the group is —CF ₂ O— can be synthesized. From bromide (i5), compound (i4) and base (B ⁻ ), compound (1D) having —CH ₂ O— in the bonding group can be synthesized. Compound (1E) in which the bonding group is —CH═CH— can be synthesized by acting aldehyde (i7) on ylide obtained from phosphonium salt (i6) and a base to carry out Wittig reaction. The salt (i6) can be synthesized by acting PPh ₃ on the bromide (i5). Compound (1F) in which the bonding group is —CH ₂ CH ₂ — can be synthesized by reducing compound (1E). By fluorinating the diketone (i8) with a fluorine anion, the compound (1G) in which the bonding group is —CF ₂ CF ₂ — can be synthesized. Since the reaction proceeds in two steps, the compound (i9) in which the bonding group is —CF ₂ CO— can be removed by adjusting the titer of the fluorine anion. By sequentially reacting the lithiated compounds (i10) and (i11) with tetrafluoroethylene, the compound (1H) in which the bonding group is —CF═CF— can be synthesized. 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) can be synthesized by the route of Formula 2. A compound (1K) in which the bonding group is —CH═CHCOO— can be synthesized by a dehydration condensation reaction between the carboxylic acid (i14) and the compound (i4). Carboxylic acid (i14) can be synthesized by Wittig reaction of aldehyde (i13). The compound (1L) in which the bonding group is —CH ₂ CH ₂ COO— can be synthesized by reduction of the compound (1K), and further the carbonyl group is fluorinated with a fluorine anion, so that the bonding group is —CH ₂ CH ₂ CF ₂ A compound (1M) which is 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) and the compound (i4). Furthermore, by fluorinating the carbonyl group with a fluorine anion, the compound (1P) in which the bonding group is —C≡CCF ₂ O— can be synthesized. Carboxylic acid (i15) can be synthesized by lithiating alkyne (i12) and acting on CO ₂ .

Compounds (1Q) to (1S) can be synthesized by the route shown in Chemical Formula 3. Compound (1Q) having a — (CH ₂ ) ₃ O— group can be synthesized from bromide (i16), compound (i4) and a base. Compound (1R) in which the bonding group is — (CH ₂ ) ₂ CH═CH— can be synthesized by acting aldehyde (i7) on ylide obtained from phosphonium salt (i17) and a base to perform Wittig reaction. Compound (1S) in which the bonding group is — (CH ₂ ) ₄ — can be synthesized by reducing compound (1R). The salt (i17) can be synthesized by acting PPh ₃ on the bromide (i16). Compound (1T) having a —CH═CHCH ₂ O— group can be synthesized from chloride (i18), compound (i4) and a base.

  The spiral direction of the compound (1) or the composition containing the compound may be any, and the circularly polarized light separating element produced therefrom selectively reflects the left circularly polarized light or the right circularly polarized light according to the direction of the spiral.

Among the compounds that can be synthesized by the above method, specific examples of preferred compounds are compounds (1-1) to (1-6). ^{However, Z 11} and ^{Z 21} is -CO -, - COO -, - CH 2 O- are ^{shown, Z 12, Z 13, Z} 22, Z 23 represents the same meaning Z and shown in section 1, R ^e1 and ^{Re2 each} represent —Y—R ^a or R ^b . The six-membered ring X has the following ring structure.

  In the above ring structure, there is no distinction between right and left of the bonding position, and any may be used.

Among the rings X ^{11 to} X ^23, a particularly preferable structure is the following structure. In the following ring structure, there is no distinction between the right and left of the bonding position, and either may be used.

More preferred Z ¹¹ and Z ²¹ are —CO— and —COO—.

Preferred Z ¹² , Z ¹³ , Z ²² and Z ²³ are a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —C═C—. Particularly preferred are a single bond, —COO—, —, and —CH ₂ O—.

  Of the compounds (1-1) to (1-6), compounds (1-1) to (1-2) and (1-4) to (1-6) are particularly preferable.

  The second aspect of the present invention is a liquid crystal composition containing two or more compounds, at least one of which is the compound (1). Preferred are at least one compound (1) and a polymerizable liquid crystal or non-polymerizable liquid crystal composition.

Particularly preferred as the polymerizable liquid crystal is at least one polymerizable compound selected from the compounds (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 Formula (M1) and Formula (M2), P ¹ is independently any one of the compounds represented by Formulas (P9) to (P12); W is hydrogen, halogen, or carbon number 1 to 3 R ^b is independently hydrogen, fluorine, chlorine, —CN, or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, — COO—, or —OCO— may be replaced, 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 fluorene-2,7-diyl, but any hydrogen is halogen, carbon number 1 ~ 3 alkyl, young Or an alkyl halide having 1 to 3 carbon atoms; X ^a is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is — O -, - COO- or -OCO- may be replaced by; 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-; s is independently an integer from 1 to 3.

  Among the compounds (M1) and (M2), preferred compounds are the formulas (M1a) to (M2c). The preferable content of the compound (M1a) to the formula (M2c) is 10 to 99% by weight, and more preferably 50 to 95% by weight.

  Particularly preferred as the non-polymerizable liquid crystal is at least one non-polymerizable compound selected from the compound (M3).

^{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, in which any —CH ₂ — is — O—, —S—, —CO—, —CH═CH—, —CF═CF—, —C≡C—, or —SiH ₂ — may be substituted, and any hydrogen is replaced with halogen. A ^c 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 — is —O—, —S—, —CO—, or —SiH ₂ —. May be replaced by any —CH ₂ CH ₂ — may be replaced by —CH═CH—, in 1,4-phenylene any —CH═ may be replaced by —N═, and in these rings any hydrogen is halogen, _{-CF 3, -CHF 2, -CH 2} F, -OCF 3, -OCHF 2, or may be replaced by -OCH ₂ F; 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 with a halogen; and n is 2, 3 or 4.

  Among the compounds (M3), preferred compounds are compounds (2) to (14). The preferred content of compounds (2) to (14) is 0.1 to 20% by weight, more preferably 0.1 to 5% by weight.

  For the purpose of improving physical properties, a non-liquid crystalline polymerizable compound, a polymerization initiator, a solvent, a surfactant, an antioxidant, a filler, an ultraviolet absorber, a sensitizer, etc. are added to the composition of the present invention. Also good. The chemical structure and composition of the additive are not limited. Furthermore, a polymerizable liquid crystal compound and a non-polymerizable compound may be mixed. Content of each component is a grade which does not impair the liquid crystallinity of a composition. Examples of known non-polymerizable liquid crystal compounds other than (M3) include a database LiqCryst (registered trademark, LCI Publisher, Hamburg, Germany) and compounds described in the publications thereof.

In order to optimize the characteristics of the composition, an optically active compound other than the compound (1) may be added. Preferable examples of the optically active compound are formulas (OP-1) to (OP-24). However, Ak represents alkyl and alkoxy having 1 to 15 carbon atoms, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. Polymerizable group P ² is a group represented by the following. t is an integer of 2-8.

  The third of the present invention is a polymer that can be produced by radical polymerization or cationic polymerization of the compound (1) or a liquid crystal composition containing them. The polymer is a linear or side chain polymer having a helical structure. When only one of the compounds (1) is polymerized, a homopolymer is obtained. A copolymer is obtained from the composition containing a plurality of polymerizable compounds.

  A mixture of 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 the present composition on a substrate by coating, irradiating with light and polymerizing. 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 can be graded by a person skilled in the art with reference to the prior art.

  Polymerization can be performed by irradiating energy (electromagnetic waves). Such electromagnetic waves are ultraviolet rays, infrared rays, visible rays, X-rays, and γ rays. Further, 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.

  A polymerizable compound having no liquid crystallinity may be added for the purpose of adjusting mechanical strength, thermal strength, coatability, orientation, and the like. (Meth) acrylate compounds, vinyl compounds, styrene compounds, vinyl ether compounds, oxirane compounds and oxetane compounds are preferred. Multifunctional acrylates, vinyl ethers, oxiranes, and oxetanes may be used to further increase the mechanical and thermal strength of the polymer.

  A surfactant may be added to facilitate application or control the alignment of the liquid crystal. 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 photo radical polymerization initiators are 1173 and 4265 from Darocur series of Ciba Specialty Co., Ltd., 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 from Irgacure series. , And 2959, but any known one can be used.

  Other examples of photo radical polymerization initiators 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 / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine A mixture, etc. It can also be used to shift.

  Examples of the cationic photopolymerization initiator include UCC Co., Ltd., Syracure UVI-6990 and 6974, Asahi Denka Co., Ltd., Adekaoptomer SP-150, 152, 170 and 172, Rhodia Co., Ltd. Photoinitiator 2074, Ciba Specialty Co., Ltd. Irgacure 250, Midori Chemical Co., Ltd. DTS-102, etc., but any known one can be used.

  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 composition of the present invention can also be applied by dissolving in a solvent. 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 Etc. can be used as a single solvent or a plurality of mixed solvents.

  In order to facilitate handling during use 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 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 applied by spreading and removing the solvent.

  If the substrate surface is subjected to orientation treatment 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. Alternatively, the substrate may be directly rubbed with a rayon cloth or the like. In some cases, the substrate surface may not be treated.

  The orientation of the composition can be fixed by irradiation with electromagnetic waves. 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 substrate. If it superposes | polymerizes, the molded object which has twist orientation can be manufactured. It has a circularly polarized light separation function in light having a wavelength (λ) that satisfies the expression “λ = refractive index × spiral pitch”. This can be used as a brightness enhancement film. The spiral direction and pitch can be optimized by appropriately selecting the type and amount of the optically active compound.

  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 0.5-1 micrometer. A preferable retardation value is 0.05 to 50 μm, more preferably 0.1 to 20 μm, and still more 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.

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 weight of ^{5 × 10 2 ~1 × 10 6} , preferably is ^{1 × 10 3 ~5 × 10 4} , more preferably ^{5 × 10 3 ~1 × 10 5} .

  Thermosetting resins can be used for polarizing plates, optical compensators, brightness enhancement films, negative c-plates and the like for liquid crystal display elements. 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.

  A fourth aspect of the present invention is a liquid crystal display device comprising as a component a composition prepared from the compound (1) or a non-polymerizable liquid crystal composition containing them. The composition used for the liquid crystal display element of the present invention is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating. Appropriate additives may be added to the composition to adjust the physical properties of the composition. Such additives are well known to those skilled in the art. A composition for a GH device may be prepared by adding a dichroic dye which is a compound such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. Compound (1) is added as a chiral dopant for the purpose of inducing a helical structure of liquid crystal to give a necessary twist angle. Compounds other than those of the present application may be added, and preferred examples thereof are the optically active compounds (Op-1) to (Op-12).

  A chiral dopant is added to the composition to adjust the twist pitch. 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. A relatively large amount of chiral dopant is added to the composition for the PC element. At least two chiral dopants may be added for the purpose of adjusting the temperature dependence of the pitch.

Hereinafter, the present invention will be described in detail by way of examples. The phase transition temperature was measured with a melting point measuring apparatus equipped with a polarizing microscope and DSC. The chemical structure of the synthesized compound was confirmed by 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).

Synthesis of the following compound (1R, 2R)-(1-2-16)

(First stage)
Under a nitrogen atmosphere, (1R, 2R)-(+)-cyclohexanecarboxylic anhydride (ex1-1) 1.0 g (6.5 mmol), 4-hexyloxyphenol 1.3 g (6.5 mmol), and a catalytic amount The pyridine was mixed, heated and melted, and stirred for 1 hour. After allowing to cool, the residue was purified by column chromatography to obtain 1.5 g (4.3 mmol) of (1R, 2R)-(−)-cyclohexanecarboxylic acid (4-hexyloxyphenyl) (ex1-2).

(Second stage)
4-N, N-dimethylaminopyridine was added to a solution of 1.5 g (4.3 mmol) of (ex1-2) obtained earlier and 0.8 g (4.1 mmol) of 4-hexyloxyphenol in 20 ml of dichloromethane under a nitrogen atmosphere. 0.6 g (4.9 mmol) of 5 ml of dichloromethane was added and stirred at room temperature for 1 hour. A solution of 1.0 g (4.9 mmol) of dicyclohexylcarbodiimide in 5 ml of dichloromethane was added and stirred at room temperature for 10 hours. Diethyl ether was added, insolubles were filtered off, and the filtrate was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and 1.5 g of bis (4-hexyloxyphenyl) bis (4-hexyloxyphenyl) (1R, 2R)-(−)-cyclohexanecarboxylate as the target product was obtained. 9 mmol) was obtained.

According to the method of Example 1, (1-6-30) is produced from compound (1-1-1). These compounds are summarized in Tables 1-12. The abbreviations in R ^e1 and R ^e2 are compared with the structure below.

A composition prepared by dissolving 1% by weight of the compound (1-2-16) produced in Example 1 in ZLI-1132 was prepared, and at 25 ° C. according to the Cano wedge method (Applied Physics, 1974, 43, 125). The helical pitch was measured. It was 16.1 micrometer ^-1 when HTP was computed from the obtained value.

The HTPs obtained according to the method of Example 2 are summarized in Table 13 together with the melting points. The compound number in a table | surface shows the compound number of Tables 1-12. The configuration of the asymmetric carbon on 1,2-cyclohexylene to which Z ¹¹ and Z ¹² are bonded is R.

The molded product obtained by polymerizing the liquid crystal composition in addition to the liquid crystal composition and the liquid crystal display element is a polarizing plate, an optical compensation plate, a brightness enhancement film, an alignment film, a color filter, a holographic element, a liquid crystal display element, an adhesive, The present invention can be applied to synthetic polymers having mechanical anisotropy, cosmetics, decorations, anti-counterfeiting devices, nonlinear optical elements, optical storage elements, and the like.

Claims (32)

An optically active compound represented by the following formula (1).

-Z- (AZ) r-Y- ^Ra (T1)
-Z- (AZ) r- ^Rb (T2)

Here, Q ¹ and Q ² are independently a group represented by the formula (T1) or (T2); R ^a is any of the polymerizable group represented by formula (P1) ~ (P8) W is independently hydrogen, halogen, C 1-3 alkyl or C 1-3 fluoroalkyl; R ^b is hydrogen, halogen, —CN, or C 1-10 alkyl. And in this alkyl any —CH ₂ — may be replaced by —O—, —S—, —CO—, —CH═CH—, or —C≡C—, and any hydrogen may be halogen or May be replaced by CN; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6- Diyl, optional in these rings -CH ₂ - may be replaced by -O-, arbitrary -CH = may be replaced by -N =, optional hydrogen halogen in these rings, an alkyl or C1-5 atoms Z may independently be a single bond or alkylene having 1 to 20 carbons, in which any —CH ₂ — represents —O—, -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen may be replaced by halogen; Y Is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — may be replaced by —O—, —S—, —COO—, or —OCO—. Well; r is It is an integer of 1-5. 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═ represents —N The optically active compound according to claim 1, wherein any hydrogen in these rings 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 20 carbon atoms, in which any —CH ₂ — is replaced by —O—, —CO—, —COO— or —OCO—. The optically active compound according to claim 1, wherein any hydrogen may be replaced by a halogen. Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — may be replaced by —O—, —COO—, or —OCO—. The optically active compound according to any one of 1 to 3. r is 1, The optically active compound according to any one of claims 1 to 4. The optically active compound according to any one of claims 1 to 4, wherein r is 2. r is 3, The optically active compound according to any one of claims 1 to 4. The optically active compound according to any one of claims 1 to 7, wherein Q ¹ and Q ² are each independently any group represented by the formula (T1). The optically active compound according to any one of claims 1 to 8, wherein ^Ra is any one of groups represented by formulas (P2) to (P6). The optically active compound according to any one of claims 1 to 9, wherein W is hydrogen, fluorine, chlorine, methyl, ethyl, or trifluoromethyl. The optically active compound according to any one of claims 1 to 7, wherein Q ¹ and Q ² are each independently any group represented by the formula (T2). R ^b is hydrogen, fluorine, chlorine, —CN or alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O—, —CO— or —CH═CH—. The optically active compound according to claim 1, wherein any hydrogen may be replaced by —F or —CN. A liquid crystal composition comprising at least two compounds, wherein at least one compound is the compound according to any one of claims 1 to 12. The compound selected from the compound of any one of Claims 1-12 is 3 to 90 weight%, and was selected from the compound represented by Formula (M1) and (M2) as another compound. The liquid crystal composition according to claim 13, which is a compound containing 10 to 97% by weight of at least one compound.
^{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)

Here, P ¹ is any of the groups represented by 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, or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, —COO—, or —OCO—. Any hydrogen may be replaced by 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 is halogen, alkyl having 1 to 3 carbons, or carbon Number 1 to 3 halogene It may be replaced by an alkyl; independently X ^a, single bond, or an alkylene having 1 to 20 carbon atoms, arbitrary _-CH 2 - in the alkylene may, -O -, - COO- or Z ^a may independently be 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 is; s is Independently, it is an integer of 1 to 3. The liquid crystal composition according to claim 13 or 14, wherein all of the compounds are polymerizable compounds. At least one polymerizable compound selected from the compounds represented by formula (M1) or (M2) is represented by formula (M1a), (M1b), (M1c), (M2a), (M2b), or (M2c). The liquid crystal composition according to claim 14, which is a compound represented by the formula:

Here, P ¹ is independently a group represented by Formulas (P9) to (P12); R ^c is independently hydrogen, fluorine, chlorine, —CN, or alkyl having 1 to 20 carbons. And in this alkyl, any —CH ₂ — may be replaced with —O—, —COO—, or OCO—, and any hydrogen may be replaced with halogen; A ^b independently , 1,4-cyclohexylene to be xylene or 1,4-phenylene,; ^{W 2} is independently halogen, alkyl having 1 to 3 carbon atoms, or a halogenated alkyl having 1 to 3 carbon atoms; X ^a is Independently a single bond, alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—; Independently, 0 or 1 and m is 0-5. Is a number. The polymer obtained by superposing | polymerizing the composition of any one of Claims 13-16. The polymer according to claim 17, which has a weight average molecular weight of 500 to 1,000,000. The polymer according to claim 17, which has a weight average molecular weight of 1,000 to 500,000. A molded article having optical anisotropy obtained by orienting the composition according to any one of claims 13 to 16 and then fixing the orientation of liquid crystal by irradiation with electromagnetic waves. The molded article according to claim 20, wherein the orientation of the fixed liquid crystal is twist orientation. An optical element comprising the molded article according to claim 20 or claim 21. The optical element according to claim 22, 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. The optical element according to claim 22, which exhibits circular dichroism in an ultraviolet region having a wavelength of 100 to 350 nm. A liquid crystal display element comprising at least one selected from the polymer according to claim 17 to 19, the molded article according to claims 20 and 21, and the optical element according to claims 22 to 24. The liquid crystal composition according to claim 13, wherein all of the compounds are non-polymerizable compounds. 0.1 to 20% by weight of at least one of the compounds according to any one of claims 1 to 7 and claims 11 to 12, and 80 to 99.9% by weight of a compound represented by the formula (M3) The liquid crystal composition according to claim 26, comprising at least one compound selected from the group consisting of:
^{R d - (A c -Z b} ) n-R d (M3)
Here, R ^d is hydrogen, halogen, —C≡C—CN, —CN, or alkyl having 1 to 20 carbons, and in this alkyl, arbitrary —CH ₂ — is —O—, —S—, —CO—, —CH═CH—, —CF═CF—, —C≡C—, or SiH ₂ — may be substituted, and any hydrogen may be replaced with a 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 any of —CH ₂ — in these rings may be replaced by —O—, —S—, —CO—, or SiH ₂ —, and any — CH ₂ CH ₂ — is —CH═CH -, And in 1,4-phenylene any —CH═ may be replaced by —N═, and in these rings any hydrogen is 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 an alkylene having 1 to 4 carbon atoms, and in this alkylene, any —CH _2- may be replaced by —O—, —S—, —CH═CH—, —CF═CF—, —C≡C—, —CO—, or SiH ₂ —, and any hydrogen may be halogenated And n is 2, 3 or 4. 28. The liquid crystal composition according to claim 27, wherein at least one compound selected from compounds represented by formula (M3) is a compound represented by formula (2), (3) or (4).

Here, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen May be replaced by 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 And 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 _{) 4 -, - COO -,} - CF 2 O -, - OCF 2 -, - CH = CH-, or a single bond; and ^{L 1} and ^{L 2} are independently hydrogen or fluorine. 29. The liquid crystal composition according to claim 27 or 28, wherein at least one compound selected from compounds represented by formula (M3) is a compound represented by formula (5) or (6).

Here, R ² and R ³ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and X ² may be —CN or —C≡C—CN; Ring G may be 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 Yes; 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 ^{Yes; L} 3, L ⁴ you Fine and L ⁵ are independently hydrogen or fluorine; and b, c and d are independently 0 or 1. The at least one compound selected from the compounds represented by the formula (M3) is a compound represented by the formula (7), (8), (9), (10) or (11): The liquid crystal composition according to any one of the above.

Here, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH— Hydrogen may be replaced by fluorine and R ⁵ may independently be fluorine; ring M and ring P are independently 1,4-cyclohexylene, 1,4-phenylene or decahydro- 2,6-naphthylene; 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. However, at least one of L ⁶ and L ⁷ is fluorine. The liquid crystal composition according to any one of claims 27 to 30, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13) and (14).

Here, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, And any hydrogen may be replaced by fluorine; ring Q, ring T and ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or any hydrogen is replaced by fluorine. And Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. . The liquid crystal display element containing the liquid-crystal composition of any one of Claims 27-31.