JP4802479B2 - Polymerizable binaphthalene derivative - Google Patents

Description

  The present invention relates to an optically active compound having a 1,1′-binaphthalene ring and a polymerizable group, a liquid crystal composition containing the compound, a polymer obtained by polymerizing the optically active compound and the liquid crystal composition, and a polymer. Regarding usage. This polymer is a molded article having optical anisotropy, and 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 difference, and the like containing the molded article. It can be used for synthetic polymers having a directivity, cosmetics, ornaments, anti-counterfeiting devices, nonlinear optical elements, optical memory elements, and the like.

In recent years, polymerizable liquid crystalline compounds have been used for molded articles having optical anisotropy. These have optical anisotropy in the liquid crystal state, and the orientation of the liquid crystalline compound is fixed by polymerization.
A helical structure is induced by adding an optically active compound to a polymerizable liquid crystal composition, but there are applications as various optical elements depending on the helical pitch. That is, the propagation of light along the helical axis depends on the target wavelength (λ) and the length (P) of the helical pitch, when (1) λ << P and (2) λ≈P. Divided into applications.

When the target λ is visible light, (1) In the case of λ << P, it corresponds to 1 (μm) <P. The application in this case is further divided into a case where the Morgan condition is satisfied and a case where the Morgan condition is not satisfied. (A) When the Morgan condition is satisfied, that is, when Φ << 2πΔnd / λ is satisfied, linearly polarized light that coincides with or is orthogonal to the optical axis direction on the incident side is emitted as linearly polarized light and functions as an optical rotator To do. Here, Φ is the total twist angle, d is the thickness, and Δn is the birefringence of the liquid crystal. (B) When the Morgan condition is not satisfied, the linearly polarized light exhibits birefringence determined by Φ, d, and Δn.
The optical rotator can be applied as an optical element for a head-up display or a projector. Further, as an application of twisted orientation birefringence, for example, there is optical compensation in an STN (Super Twisted Nematic) liquid crystal display (see Patent Document 1).

Assuming that the target λ is visible light, (2) when λ≈P, for example, when the twist direction of the spiral structure is right, the liquid crystal film is no × P <λ <ne × P (no is a liquid crystal The refractive index of the layer with respect to ordinary light, and ne is the refractive index with respect to the extraordinary light of the liquid crystal layer). Or, all the left-handed circularly polarized light of all wavelengths is transmitted. That is, it is possible to selectively separate right circularly polarized light and left circularly polarized light having a specific wavelength (circular dichroism). Specifically, from the viewpoint of application of the optical element, (A) 350 / n _ave (nm) <P ≦ 800 / n _ave (nm), that is, the wavelength region of circular dichroism is in the visible light region. And (B) P <350 / n _ave (nm), that is, when the wavelength region of circular dichroism is in the ultraviolet region. (N _ave = ((ne ² + no ² ) / 2) ^0.5

(A) In the case of 350 / n _ave (nm) <P ≦ 800 / n _ave (nm), when non-polarized light is incident, coloring occurs in reflected light and transmitted light according to the wavelength that causes circular dichroism. . If such coloring is used, it can be applied to design applications such as decorative members and color filters used in liquid crystal display elements. In addition, the reflected and transmitted light has a unique metallic luster, the color tone changes depending on the viewing angle, and these optical characteristics cannot be duplicated by ordinary copying machines, so it can be applied to anti-counterfeiting applications. It is. Further, it is possible to improve the light utilization efficiency in the liquid crystal display element by applying such a circularly polarized light separation function. For example, a configuration in which a 1 / 4λ plate and an optically anisotropic film that exhibits a circularly polarized light separation function are stacked on a polarizing plate has been proposed (see Non-Patent Document 1). For such applications, it is desired that the circularly polarized light separation function is expressed in the entire visible light region (wavelength range of 350 to 750 nm). The pitch may be continuously changed in the direction. The reflection spectral width Δλ is wider as the birefringence anisotropy value (Δn) is larger from the relational expression Δλ = Δn × P. The center wavelength λc of the reflection spectrum is calculated from the relational expression of λc = n _ave × P.
In addition, if a similar circularly polarized light separation function is used and a range of 700 / n _ave (nm) <P ≦ 1.5 / n _ave (μm) is set, it is possible to apply an ultraviolet or near-infrared reflection filter. .

(B) In the case of P ≦ 350 / n _ave (nm), the refractive index of the visible light region with respect to the surface perpendicular to the helical axis is represented by ((ne ² + no ² ) / 2) ^0.5 , and the helical axis The refractive index in the visible light region with respect to the direction is equal to no (see Non-Patent Document 2).

  An optically anisotropic film having such optical characteristics is called a negative C-plate. In a liquid crystal display element that obtains a black display (dark state) when liquid crystal molecules having positive birefringence are aligned perpendicular to the substrate, birefringence due to the alignment of the liquid crystal molecules with respect to the normal direction of the display element Does not occur. Therefore, in these display elements, a very high contrast is obtained in the normal direction. However, when it deviates from the normal direction of the display element, birefringence occurs and the transmittance of black display (dark state) increases. That is, in these display elements, the contrast decreases with respect to the oblique viewing angle. The negative C-plate can compensate for the birefringence that occurs when such a display element deviates from the normal direction of the liquid crystal alignment. As a result, this negative C-plate is an optical compensation plate suitable for improving viewing angle characteristics in display elements such as VA (Vertical Aligned), TN (Twisted Nematic), OCB (Optically Compensated Birefringence), and HAN (Hybrid Aligned Nematic). It becomes.

  Currently, a compressed polymer film or a planar film-oriented film using a discotic liquid crystal having negative birefringence (see Patent Document 2) is used as an optical compensator. By utilizing a polymer of cholesteric liquid crystal composed of liquid crystal molecules having positive birefringence, the degree of freedom in designing the refractive index anisotropy value and its wavelength dispersion is expanded. The negative C-plate can be used in combination with various optical compensation layers.

The pitch and Δn are adjusted as appropriate for the optical design for each application.
For any of the above applications, as a pre-curing property for photopolymerizable liquid crystals, it has a nematic phase at room temperature, has a wide nematic phase, exhibits good orientation, and is fast-cured by UV irradiation. Development of a photopolymerizable cholesteric liquid crystal composition having an appropriate Δn as a characteristic after curing, transparency, excellent heat resistance and moisture resistance is desired.
In addition, when optimizing a compound, in addition to the above optical characteristics, 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.

A helical structure is induced by adding an optically active compound to the liquid crystal composition (see Patent Document 3 or 4). 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) and the like.

  In any application, it is preferable to minimize the addition amount of the optically active compound so that other physical properties such as viscosity and liquid crystal properties 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.

  When applied to polarizing plates, optical compensators such as N-type c-plates, alignment films, color filters, adhesives, synthetic polymers having mechanical anisotropy, cosmetics, ornaments, anti-counterfeiting devices, etc. Utilize a molded body with directionality. 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 polymerization rate.

JP-A-8-87008 (US5599478) JP 2002-6138 A (US66885998) British Patent Application No. 2298202 International Publication No. 02/28985 Pamphlet Y. Hisatake et al, Asia Display / IDW '01 LCT8-2 W. H. de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980)

  The first object of the present invention is to provide a liquid crystalline compound having a large HTP, excellent solubility in other liquid crystal compounds, high polymerizability and having a 1,1′-binaphthalene ring, and a liquid crystal composition containing this compound Is to provide things. 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 many characteristics such as, and a molded article having optical anisotropy produced from this 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, an optical storage element, and the like.

The present invention includes at least one compound represented by the following formula (1), a liquid crystal composition containing the compound, and a polymer obtained by polymerizing the compound or the composition.

In the formula (1), Q ^{1 to} Q ⁴ are independently the formula (2), hydrogen, halogen, or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O -, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and any hydrogen may be replaced by halogen, Q ¹ -Q ^At least two of ⁴ are the formula (2) which may represent different groups; in the formula (2), A is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4 -Cyclohexenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, bicyclo [2.2.2] octane-1,4-diyl, naphthalene-2,6 -Diyl, tetrahydronaphthalene-2,6-dii , Decalin-2,6-diyl, or 1,3-dioxane-2,5-diyl, wherein any hydrogen of these rings is halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms X is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —S—, —COO— or It may be replaced by -OCO-, and arbitrary hydrogen may be replaced by fluorine; 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 -, - CF 2 CF 2 -, - CH = CH -, - CH = CHCH 2 CH _{2 -, - CH 2 CH 2} CH = CH -, - C _{= CHCH 2 O -, - OCH} 2 CH = CH -, - CF = CF -, - C≡C -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 CF 2 O -, - OCF 2 CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —C≡CCOO—, or —OCOC≡C—; n is , An integer of 0 to 3, and when n is 1, 2 or 3, the plurality of A may be the same group or different groups, and when n is 2 or 3 The plurality of Z may be the same group or different groups; P is any one of the polymerizable groups represented by formulas (P1) to (P8); Is hydrogen, halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms. It is a kill. However, when Q ¹ and Q ² are both hydrogen, and Q ³ and Q ⁴ are both formulas (2), P is not (P8).

  Compound (1) has a large helical induction force. Compound (1) can be polymerized by irradiation with electromagnetic waves. Compound (1) is excellent in solubility with other liquid crystal compounds, and lowers the crystallization temperature of the composition obtained by mixing the two. The polymer obtained from the liquid crystal composition containing the compound (1) has transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, gas permeability, melting point, glass transition. Excellent in many characteristics such as point, clear point, heat resistance and chemical resistance. The polymer obtained from the liquid crystal composition containing the compound (1) has 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, and mechanical anisotropy. It can be used for synthetic polymers, cosmetics, decorations, anti-counterfeiting devices, nonlinear optical elements, optical memory elements, and the like.

  Terms used in this specification are as follows. 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 term “arbitrary” means “can be freely selected not only in position but also in number”. For example, the expression “any A may be replaced with B, C, D, or E” means that one A may be replaced with B, C, D, or E, and In addition to the meaning that any may be replaced by any one of B, C, D and E, A replaced by B, A replaced by C, A replaced by D, and E replaced It also means that at least two of A may be mixed. The meaning of the phrase “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-. 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.

  As a result of studies conducted by the present inventors to achieve the above object, the liquid crystal compound having a 1,1′-binaphthalene ring of the present invention has a large HTP, excellent polymerizability, and compatibility with other compounds. I found that it is excellent. In addition, the present inventors have found that the liquid crystal composition containing the compound of the present invention is excellent in coating properties, orientation properties, polymerizability, etc., and the polymer is a reflective polarizing plate, a retardation plate, a brightness enhancement film, The present invention was completed by finding that it is excellent as an optical functional thin film such as a negative c-plate. The present invention is as described in the following items [1] to [26].

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

In the formula (1), Q ^{1 to} Q ⁴ are independently the formula (2), hydrogen, halogen, or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O -, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and any hydrogen may be replaced by halogen, Q ¹ -Q ^At least two of ⁴ are the formula (2) which may represent different groups; in the formula (2), A is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4 -Cyclohexenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, bicyclo [2.2.2] octane-1,4-diyl, naphthalene-2,6 -Diyl, tetrahydronaphthalene-2,6-dii , Decalin-2,6-diyl, or 1,3-dioxane-2,5-diyl, wherein any hydrogen of these rings is halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms X is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —S—, —COO— or It may be replaced by -OCO-, and arbitrary hydrogen may be replaced by fluorine; 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 -, - CF 2 CF 2 -, - CH = CH -, - CH = CHCH 2 CH _{2 -, - CH 2 CH 2} CH = CH -, - C _{= CHCH 2 O -, - OCH} 2 CH = CH -, - CF = CF -, - C≡C -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 CF 2 O -, - OCF 2 CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —C≡CCOO—, or —OCOC≡C—; n is , An integer of 0 to 3, and when n is 1, 2 or 3, the plurality of A may be the same group or different groups, and when n is 2 or 3 The plurality of Z may be the same group or different groups; P is any one of the polymerizable groups represented by formulas (P1) to (P8); Is hydrogen, halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms. It is a kill. However, when Q ¹ and Q ² are both hydrogen and Q ³ and Q ⁴ are both formulas (2), P is not (P8), Q ¹ and Q ² are both hydrogen, and Q ³ and Q ⁴ In the formula (2), X adjacent to the binaphthalene ring is —OCO—, n is 0, A is 1,4-phenylene, and X adjacent to P is —O (CH ₂ ). ₄ OCH ₂ —, when P is (P2), W is not ethyl .

[2] Q ^{1 to} Q ⁴ are each independently formula (2), hydrogen, fluorine, chlorine, bromine, or alkyl having 1 to 25 carbon atoms, and any —CH ₂ — in the alkyl is — O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C— may be replaced, and any hydrogen may be replaced with a halogen; 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms Well; X is independently a single bond, —COO—, —OCO— or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—. , And any hydrogen is replaced by fluorine May; Z is a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CH = CH -, - C≡C -, - CH 2 _{CH 2 COO -, - OCOCH 2} CH 2 -, - CH = CHCOO-, or -OCOCH = a CH- [1] a compound according to claim.

[3] Formulas Q ^{1 to} Q ⁴ are independently Formula (2), hydrogen, fluorine, chlorine, bromine, or alkyl having 1 to 10 carbons, and any —CH ₂ — in the alkyl is -O-, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and any hydrogen may be replaced by halogen; Independently, 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine, chlorine, methyl or trifluoromethyl; X is independently A single bond or alkylene having 1 to 10 carbon atoms, in which any —CH ₂ — may be replaced by —O—, and any hydrogen may be replaced by fluorine; , Single bond, -COO-, -OC _{-, - CH 2 CH 2 -} , - CH 2 O -, - OCH 2 -, - C≡C -, - CH = CHCOO-, or -OCOCH = a CH- [1] A compound according to claim.

[4] In the formula (2) described in the item [1], P is the formula (P2), (P3), (P5), (P6), (P7), or (P8) [2] or The compound according to item [3].

[5] In the formula (2) described in the item [1], P is the formula (P2), (P3), (P6), (P7), or (P8) [2] or [3] Compound described in 1.

[6] The compound according to [2] or [3], wherein P is the formula (P2) in the formula (2) according to the item [1].

[7] Q ¹ and Q ² are independently halogen or alkyl having 1 to 30 carbons, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, — OCO—, —CH═CH—, or —C≡C— may be substituted, and any hydrogen may be substituted with halogen, and Q ³ and Q ⁴ may each represent a different group The compound according to item [1], which is formula (2); and P is formula (P8).
[8] Q ¹ and Q ² are independently fluorine, chlorine, bromine, or alkyl having 1 to 25 carbon atoms, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C— may be substituted, and any hydrogen may be substituted with halogen, and Q ³ and Q ⁴ are each different groups. Wherein A is independently 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in these rings is halogen, having 1 to 3 carbon atoms Alkyl or C 1-3 fluoroalkyl may be substituted; X is independently a single bond, —COO—, —OCO—, or alkylene having 1 to 10 carbon atoms, -CH ₂ - is, replace with -O- May be, and any hydrogen may be replaced by fluorine; Z is a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CHCOO-, or -OCOCH = CH- and is; P is the formula (P8) The compound according to [1].
[9] Q ¹ and Q ² are independently fluorine, chlorine, bromine, or alkyl having 1 to 10 carbons, and any —CH ₂ — in the alkyl is —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C— may be substituted, and any hydrogen may be substituted with halogen, and Q ³ and Q ⁴ are each different groups. Wherein A is independently 1,4-cyclohexylene, 1,4-phenylene, or any hydrogen replaced by fluorine, chlorine, methyl or trifluoromethyl. 1,4-phenylene; X is independently a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—; and Arbitrary hydrogen is replaced by fluorine It may be replaced; Z is a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - C≡C -, - CH = CHCOO-, Or -OCOCH = CH-; The compound according to item [1], wherein P is formula (P8).
[10] In the formula (1) described in the item [1], Q ^{1 to} Q ⁴ are each a formula (2) that may represent different groups; in the formula (2) described in the item [1], The compound according to any one of [1] to [3], wherein P is the formula (P8).

式（１）において、Ｑ^１〜Ｑ^４は独立して、式（２）、水素、ハロゲン、または炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく、Ｑ^１〜Ｑ^４の少なくとも２つはそれぞれ異なる基を表してもよい式（２）であり；式（２）において、Ａは独立して、１，４−シクロへキシレン、１，４−フェニレン、１，４−シクロヘキセニレン、ピリジン−２，５−ジイル、ピリダジン−３，６−ジイル、ピリミジン−２，５−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、デカリン−２，６−ジイイル、または１，３−ジオキサン−２，５−ジイルであり、これらの環の任意の水素がハロゲン、炭素数１〜３のアルキルまたは炭素数１〜３のフルオロアルキルで置き換えられてもよく；Ｘは独立して、単結合または炭素数１〜２０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｚは、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２ＣＦ_２Ｏ−、−ＯＣＦ_２ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−Ｃ≡ＣＣＯＯ−、または−ＯＣＯＣ≡Ｃ−であり；ｎは、０〜３の整数であり、ｎが１、２または３であるとき複数のＡはそれぞれ同一の基であってもよく、異なる基であってもよく、またｎが２または３であるとき複数のＺはそれぞれ同一の基であってもよく、異なる基であってもよく；Ｐは、式（Ｐ１）〜（Ｐ８）で表される重合性の基のいずれか１つであり；Ｗは、水素、ハロゲン、炭素数１〜３のアルキルまたは炭素数１〜３のフルオロアルキルである。ただし、Ｑ^１およびＱ^２が共に水素、かつＱ^３およびＱ^４が共に式（２）であるとき、Ｐは（Ｐ８）ではない。
[11] A liquid crystal composition comprising at least two compounds, wherein at least one compound is the compound according to any one of items [1] to [10].
[12] The liquid crystal composition according to item [11], wherein all of the compounds are polymerizable compounds.
[13] At a ratio based on the total amount of the composition, at least one of the compounds represented by the formula (1) is in the range of 0.01 to 90% by weight, and is represented by each of the formulas (M1) and (M2). A liquid crystal composition in which at least one polymerizable compound selected from the group of compounds is in the range of 10 to 99.99% by weight.

In the formula (1), Q ^{1 to} Q ⁴ are independently the formula (2), hydrogen, halogen, or alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is —O -, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C-, and any hydrogen may be replaced by halogen, Q ¹ -Q ^At least two of ⁴ are the formula (2) which may represent different groups; in the formula (2), A is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4 -Cyclohexenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, bicyclo [2.2.2] octane-1,4-diyl, naphthalene-2,6 -Diyl, tetrahydronaphthalene-2,6-dii , Decalin-2,6-diyl, or 1,3-dioxane-2,5-diyl, wherein any hydrogen of these rings is halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms X is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —S—, —COO— or It may be replaced by -OCO-, and arbitrary hydrogen may be replaced by fluorine; 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 -, - CF 2 CF 2 -, - CH = CH -, - CH = CHCH 2 CH _{2 -, - CH 2 CH 2} CH = CH -, - C _{= CHCH 2 O -, - OCH} 2 CH = CH -, - CF = CF -, - C≡C -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 CF 2 O -, - OCF 2 CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —C≡CCOO—, or —OCOC≡C—; n is , An integer of 0 to 3, and when n is 1, 2 or 3, the plurality of A may be the same group or different groups, and when n is 2 or 3 The plurality of Z may be the same group or different groups; P is any one of the polymerizable groups represented by formulas (P1) to (P8); Is hydrogen, halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms. It is a kill. However, when Q ¹ and Q ² are both hydrogen, and Q ³ and Q ⁴ are both formulas (2), P is not (P8) .

In Formula (M1) and Formula (M2), P ¹ is independently any one of the polymerizable groups represented by Formulas (P9) to (P12); W is hydrogen, halogen, carbon R ¹ is hydrogen, fluorine, chlorine, —CN or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ -May be replaced by -O-, -COO- or -OCO-, and any hydrogen may be replaced by halogen; A ¹ 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, and these Any hydrogen in the ring is Androgenic, may be replaced by an alkyl halide of 1 to 3 alkyl carbon atoms or 1 to 3 carbon atoms; X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, in the alkylene Any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; Z ¹ 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═CHCOO—, or —OCOCH═CH—; s is an integer of 1 to 3, and when s is 1, 2 or 3, the plurality of A ¹ may be the same group or different groups, and s is 2 or When Z is 3, a plurality of Z ¹ may each be the same group, Different groups may be used.

[14] At least one polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2) is represented by any one of formulas (M1a) to (M2c) The liquid crystal composition according to item [13], which is a compound.

In formulas (M1a) to (M2c), P ¹ is any one of polymerizable groups represented by formulas (P9) to (P12); R ¹ is hydrogen, fluorine, chlorine, —CN , Or alkyl having 1 to 20 carbons, in which arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—, and optional hydrogen is replaced by halogen Ring A ² is independently 1,4-cyclohexylene or 1,4-phenylene, and W ¹ is independently hydrogen, halogen, C 1-3 alkyl or carbon X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —COO— or May be replaced by -OCO- p and q are independently 0 or 1, m is independently an integer of 0 to 5.

[15] A polymer obtained by polymerizing at least one of the compounds according to item [1].
[16] A polymer obtained by polymerizing the composition according to any one of items [11] to [14].
[17] The polymer according to [15] or [16], wherein the weight average molecular weight is 500 to 1,000,000.
[18] The polymer according to item [15] or [16], wherein the weight average molecular weight is 1,000 to 500,000.

[19] After aligning at least one of the compounds described in [1] or the liquid crystal composition described in any one of [11] to [14], the compound or composition is irradiated with electromagnetic waves. A molded article having optical anisotropy obtained by fixing the alignment state of liquid crystal by polymerizing the product.
[20] The molded article according to item [19], wherein the alignment state of the fixed liquid crystal is twist alignment.

[21] An optical element comprising the molded article according to the item [19] or [20].
[22] The optical element according to item [21], which has a helical pitch of 1 nm or more and less than 200 nm.
[23] The optical element according to the item [21], which exhibits circular dichroism for light having a wavelength in a part or all of the wavelength range of 350 to 750 nm.
[24] The optical element according to item [21], which exhibits circular dichroism in an ultraviolet light region having a wavelength of 100 to 350 nm.

[25] The polymer according to any one of items [15] to [18], the molded article according to item [19] or [20], and any one of items [21] to [24]. A liquid crystal display element comprising at least one selected from the group of optical elements described in 1.

[26] In Formula (1), Q ¹ and Q ² are hydrogen, Q ³ and Q ⁴ are independently Formula (2 ′), and in Formula (2 ′), A is independently 1, 4-cyclohexylene or 1,4-phenylene, Z is a single bond or —OCO—, W is methyl or ethyl, y is an integer of 2 to 10, and n is 1 or 2. The compound according to item [1], which is 2.

The first of the present invention is an optically active compound having a 1,1′-binaphthalene ring represented by formula (1) and a polymerizable group. Q ^{1 to} Q ⁴ in the formula are independently Formula (2), hydrogen, halogen, or alkyl having 1 to 30 carbons, and any —CH ₂ — in the alkyl is —O—, —S. -, -COO-, -OCO-, -CH = CH-, or -C≡C- may be substituted, and any hydrogen may be replaced by a halogen. ^Then, at least 2 Exemplary ethynylphenylbiadamantane derivatives of Q 1 to Q ⁴ (2), these equations (2) may represent a different group.

Preferable Q ^{1 to} Q ⁴ other than the formula (2) are hydrogen, fluorine, chlorine, bromine, and alkyl having 1 to 25 carbon atoms. Particularly preferred Q ^{1 to} Q ⁴ other than formula (2) are hydrogen, fluorine, chlorine, bromine, and alkyl having 1 to 10 carbon atoms. Any —CH ₂ — in these alkyls may be replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C—, and any Hydrogen may be replaced by halogen, and may be linear, branched or have a cyclic structure. Halogen is preferably chlorine or fluorine.
When Q ^{1 to} Q ⁴ other than the formula (2) are hydrogen, the viscosity is small. In the case of fluorine, chlorine or bromine, the dielectric anisotropy value is large. In the case of alkyl having 1 to 10 carbon atoms, liquid crystallinity is excellent. When it is an alkyl having 1 to 10 carbon atoms having —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C—, the liquid crystallinity is excellent and the dielectric constant is anisotropic. Property values and optical anisotropy values can be optimized. In the case of a C1-C10 alkyl having a halogen, the dielectric anisotropy value and the optical anisotropy value can be optimized.

  A in Formula (2) is a divalent group having a ring structure. A is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5- Diyl, bicyclo [2.2.2] octane-1,4-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl, or 1,3-dioxane- 2,5-diyl, and preferred A is 1,4-cyclohexylene and 1,4-phenylene. Any hydrogen in these rings may be replaced with halogen, alkyl having 1 to 3 carbon atoms or fluoroalkyl having 1 to 3 carbon atoms.

  Particularly preferred 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. Specific examples are as follows.

  In each formula, these rings may be bonded in the opposite directions. That is, since 2-fluoro-1,4-phenylene is structurally identical to 3-fluoro-1,4-phenylene, the latter was not exemplified. This rule also applies to the relationship between 2,6-difluoro-1,4-phenylene and 3,5-difluoro-1,4-phenylene. The steric configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans. 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 formula (2) is a linking group. 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 —, —CF ₂ CF ₂ —, —CH═CH—, —CH═CHCH ₂ CH ₂ —, —CH ₂ CH ₂ CH═CH—, —CH═CHCH ₂ O—, —OCH ₂ CH═CH—, —CF═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ CF ₂ O—, —OCF ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CHCOO—, —OCOCH═CH—, —C≡CCOO—, or —OCOC≡C—. 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—, and —OCOCH═CH— tend to improve liquid crystallinity. _-CF 2 _CF 2 with fluorocarbon _{-, - CF 2 O -,} - OCF 2 -, - CH 2 CH 2 CF 2 O-, and -OCF ₂ CH ₂ CH ₂ - may reduce the optical anisotropy, or There is a tendency to increase the dielectric anisotropy. -C≡C-, -C≡CCOO- and -OCOC≡C- having a triple bond tend to induce large optical anisotropy. Preferred Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C≡C—, —CH═CHCOO—, and —OCOCH═CH. -. Particularly preferred Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C≡C—, —CH═CHCOO—, and —OCOCH═. CH-.

X is independently a single bond, alkylene having 1 to 20 carbon atoms in which any —CH ₂ — may be replaced by —O—, —S—, —COO— or —OCO—. Preferred X is a single bond, —COO—, —OCO—, or alkylene having 1 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—. Particularly preferable X is a single bond and alkylene having 1 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—. X may have a branched structure. Arbitrary hydrogen in these X may be replaced by fluorine. Two Xs may be the same or different. Further, when it has an asymmetric carbon, it may be a racemate or an optically active substance. In the case of an optically active substance, in order not to reduce the HTP of the compound, it is necessary to use a group that induces the same twist direction as the twist direction induced from the binaphthalene structure. When it is necessary to adjust the HTP of a compound, a group that induces a twist direction opposite to the twist direction induced from the binaphthalene structure may be used.

  P is a polymerizable group represented by formulas (P1) to (P8), and W is hydrogen, halogen, alkyl having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons. Preferred W is hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl. n is an integer of 0-3. Preferred n is an integer of 0 to 2, and particularly preferred n is 1 or 2. When n is 1, the two A's may be the same or different. When n is 2, three A (or two Z) may be the same or different. The same applies when n is 3.

  The polymerizable groups (P1), (P2) and (P8) are suitable for cationic polymerization. Preferred polymerizable groups suitable for cationic polymerization are the polymerizable groups (P2) and (P8), and the particularly preferred polymerizable group is the polymerizable group (P2). The polymerizable groups (P3) to (P7) are suitable for radical polymerization. Preferred polymerizable groups suitable for radical polymerization are polymerizable groups (P3) and (P5) to (P7), and particularly preferred polymerizable groups are polymerizable groups (P3), (P6) and (P7). is there. Polymerization can be performed more rapidly by adding a polymerization initiator or optimizing the reaction temperature.

By appropriately selecting Q ^{1 to} Q ⁴ , A, Z, X, P, n, or W, a compound (1) having desired physical properties can be obtained.

  Although the liquid crystalline residue of the formula (2) can be suitably used in any structure, it is preferably (2-1) to (2-12). In the following, Ph is 1,4-phenylene which may be substituted, Ch is 1,4-cyclohexylene which may be substituted, and X and Z have the same meaning as described above.

-X-Ph-X-P (2-1)
-X-Ch-X-P (2-2)
-X-Ph-Z-Ph-XP (2-3)
-X-Ch-Z-Ph-XP (2-4)
-X-Ph-Z-Ch-XP (2-5)
-X-Ch-Z-Ch-XP (2-6)
-X-Ph-Z-Ph-Z-Ph-XP (2-7)
-X-Ch-Z-Ph-Z-Ph-XP (2-8)
-X-Ph-Z-Ch-Z-Ph-XP (2-9)
-X-Ph-Z-Ph-Z-Ch-XP (2-10)
-X-Ch-Z-Ch-Z-Ph-XP (2-11)
-X-Ph-Z-Ch-Z-Ch-XP (2-12)

  Among (2-1) to (2-12), (2) is preferably (2-3) to (2-12). Particularly preferred (2) is (2-3) and (2-7).

  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.

A preferred compound (1) is represented by formula (1), wherein Q ¹ and Q ² are hydrogen, Q ³ and Q ⁴ are independently formula (2 ′), and in formula (2 ′), A is independently 1, 4-cyclohexylene or 1,4-phenylene, Z is a single bond or —OCO—, W is methyl or ethyl, y is an integer of 2 to 10, n Is 1 or 2.

The production method of compound (1) will be described. The polymerizable groups (P4), (P6) and (P7) can be introduced by acting acrylic acid chlorides on liquid crystalline residues having an amino group and a hydroxyl group, respectively. The polymerizable group (P1) can be introduced by oxidizing a liquid crystalline residue having a cyclohexene ring. A known intermediate having a cyclohexene oxide ring may be used. The polymerizable groups (P2) and (P8) may be a known intermediate having an oxetane ring or an oxirane ring, such as 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane or epichlorohydrin. Can be introduced using. The polymerizable group (P8) can also be synthesized by oxidizing the corresponding terminal unsaturated bond. The polymerizable group (P3) can be introduced by acting maleic anhydride on a liquid crystalline residue having a hydroxyl group. The polymerizable group (P5) can be introduced by acting β-chloropropionic acid chloride on a liquid crystalline residue having a halogen and then removing HCl. However, the liquid crystalline residue is -X- (AZ) _n -AX-.

The structure of the compound (1) other than the polymerizable group is as follows: Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, It can be produced by appropriately combining organic synthetic chemical techniques described in Reactions (John & Wily & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), and the like. Specifically, it can be constructed by combining organic residues having a 6-membered ring structure. Next, the coupling method will be described. In the following, MG ¹ and MG ² are monovalent organic residues having one or more 6-membered ring structures, and may be different or the same. (1A) to (1P) are the compound (1).

Compounds (1A) to (1J) can be synthesized by the route of FIG. Compound (1A) in which Z is a single bond can be synthesized by a cross-coupling reaction of boronic acid (i1) and bromide (i2). By dehydration condensation reaction of carboxylic acid (i3) and compound (i4) having a hydroxyl group, compound (1B) in which the bonding group is —COO— can be synthesized, 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 (i12) in the presence of a transition metal catalyst.

Compounds (1K) to (1P) can be synthesized by the route of FIG. 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 of FIG. 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.

Of the compounds that can be synthesized by the above method, specific examples of preferred compounds are compounds (1-1) to (1-36). However, ^{L 1} is hydrogen, halogen or alkyl having 1 to 25 carbon atoms, any _-CH 2 in the alkyl - is -O -, - S -, - COO -, - OCO -, - CH═CH—, or —C≡C— may be replaced, and any hydrogen may be replaced with a halogen. X, Z, and W have the same meaning as shown in claim 1. However, L ¹ of the compounds (1-3) and (1-9) is not hydrogen.

Preferred L ¹ is hydrogen, bromine, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, and alkoxyalkyl having 1 to 9 carbons. Particularly preferred L ¹ is hydrogen and bromine.

Preferred X is a single bond, —COO—, —OCO—, or alkylene having 1 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—. Particularly preferred X is — (CH ₂ ) _x —, —O (CH ₂ ) _x-1 —, — (CH ₂ ) _x-1 O—, —O (CH ₂ ) _xy-2 O (CH ₂ ) _y -, and _{- (CH 2) y O (} CH 2) x-y-2 are O-, x is an integer from 1 to 10, y is an integer of 1 to 3.

Preferred Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C≡C—, —CH═CHCOO—, and —OCOCH═CH. -. The linking group linked to the 1,1′-binaphthalene ring is preferably —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CHCOO—, and —OCOCH═CH—.

Particularly preferred compounds among the compounds (1-1) to (1-36) are the compounds (1-2) to (1-5), (1-8) to (1-13), (1-29). -(1-32), (1-35), and (1-36). More preferred compounds are compounds (1-2) and (1-7) to (1-11). Further preferred compounds are those in which X linked to the 1,1′-binaphthalene ring is —OCO—, and X linked to the polymerizable group is —O (CH ₂ ) _x OCH ₂ — or —O (CH ₂ ) _x —, Z Is a single bond, —OCO— or —OCOCH═CH—, and W is methyl or ethyl, the compounds of formulas (1-2) to (1-16). However, x is an integer of 2-10.

  Particularly preferred compounds (1-2a) to (1-31d) are shown more specifically.

  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). A preferred composition is a polymerizable liquid crystal composition containing at least one compound (1) and a monofunctional polymerizable liquid crystal or a polyfunctional polymerizable liquid crystal.

  A particularly preferred compound as the monofunctional polymerizable liquid crystal or the polyfunctional polymerizable liquid crystal is at least one polymerizable compound selected from the compounds (M1) and (M2).

In formulas (M1) and (M2), P ¹ is independently any one of the polymerizable groups represented by formulas (P9) to (P12); W is hydrogen, halogen, carbon number 1 to 3 alkyl or fluoroalkyl having 1 to 3 carbon atoms; R ¹ is hydrogen, fluorine, chlorine, —CN, or alkyl having 1 to 20 carbon atoms, and in this alkyl, any —CH ₂ — May be replaced with —O—, —COO— or —OCO—, and any hydrogen may be replaced with a halogen; A ¹ 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, and these rings Any hydrogen of Gen, may be replaced by an alkyl halide of 1 to 3 alkyl carbon atoms or 1 to 3 carbon atoms; X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, in the alkylene Any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; Z ¹ represents a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CHCOO—, or —OCOCH═CH—; An integer of 1 to 3, and when s is 1, 2 or 3, the plurality of A ¹ may be the same group or different groups, and s is 2 or 3 When the plurality of Z ¹ may be the same group or different groups, There may be.

式（Ｍ１ａ）〜（Ｍ２ｃ）において、Ｐ^１は、式（Ｐ９）〜（Ｐ１２）で表される重合性の基のいずれか１つであり；Ｒ^１は、水素、フッ素、塩素、−ＣＮ、または炭素数１〜２０のアルキルであり、このアルキルにおいて、任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；環Ａ^２は独立して、１，４−シクロへキシレンまたは１，４−フェニレンであり、Ｗ^１は独立して、水素、ハロゲン、炭素数１〜３のアルキルまたは炭素数１〜３のハロゲン化アルキルであり；Ｘ^１は独立して、単結合または炭素数１〜２０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく；ｐおよびｑは独立して、０または１であり、ｍは独立して、０〜５の整数である。 Preferred compounds among the compounds (M1) and (M2) are compounds represented by the following formulas (M1a) to (M2c). The preferable content of the compound (M1a) to the formula (M2c) is in the range of 10 to 99% by weight based on the total weight of the liquid crystal composition, and the more preferable content is in the range of 50 to 95% by weight.

In formulas (M1a) to (M2c), P ¹ is any one of polymerizable groups represented by formulas (P9) to (P12); R ¹ is hydrogen, fluorine, chlorine, —CN , Or alkyl having 1 to 20 carbons, in which arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—, and optional hydrogen is replaced by halogen Ring A ² is independently 1,4-cyclohexylene or 1,4-phenylene, and W ¹ is independently hydrogen, halogen, C 1-3 alkyl or carbon X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —COO— or May be replaced by -OCO- p and q are independently 0 or 1, m is independently an integer of 0 to 5.

  For the purpose of improving physical properties, the composition of the present invention is added to a non-polymerizable liquid crystal compound, a non-liquid crystalline polymerizable compound, a polymerization initiator, a solvent, a surfactant, an antioxidant, a filler, an ultraviolet absorber, an enhancer. A sensitizer or the like may be added. The chemical structure and composition of the additive are not limited. Content of each component is a grade which does not impair the liquid crystallinity of a composition. Examples of non-polymerizable liquid crystal compounds are those described in the database LiqCryst (registered trademark, LCI Publisher, Hamburg, Germany) and 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). Here, Ak represents alkyl having 1 to 15 carbons or alkoxy having 1 to 15 carbons, 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. This 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. When a composition containing a plurality of polymerizable compounds is polymerized, a copolymer is obtained.

  The polymerizable liquid crystal composition containing the compound (1) and the nematic liquid crystal composition has 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 such as reflective polarizing plates, brightness enhancement films, color filters, ornaments, ID cards, 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, γ rays, and the like. Further, high energy particles such as ions and electrons may be irradiated.

  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 the composition of the present invention to facilitate application or to 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 in the range of 100 ppm to 5% by weight, more preferably 100 ppm to 1% by weight with respect to the liquid crystal composition of the present invention.

  Examples of the photo radical polymerization initiator are specific trade names, such as 1173 and 4265 from Ciba Specialty Chemicals' Darocur series, and 184, 369, 500, 651, 784, 819, 907 from Irgacure series. 1300, 1700, 1800, 1850, 2959, etc., but any known initiator 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. The deviation of the initiator can also be used.

  Examples of the photo-cationic polymerization initiator are specific trade names such as Syracuea UVI-6990 and 6974 from UCC, Adeka optomer SP-150, 152, 170 and 172 from Asahi Denka Kogyo Co., Ltd. Photoinitiator 2074 from Rhodia Co., Ltd., Irgacure 250 from Ciba Specialty Chemicals Co., Ltd., DTS-102 from Midori Chemical Co., Ltd., etc., but any known initiator can be used.

  The molded body of the present invention is obtained by applying the compound or composition of the present invention on a substrate to form a coating film, and polymerizing the nematic alignment formed by the composition in a liquid crystal state by irradiation with electromagnetic waves such as light. It can be manufactured by immobilization. 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 compound or composition of the present invention can be dissolved in a solvent and applied. Preferred solvents are 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 , Cyclopentanone, cyclohexanone, etc. Single solvent of a mixed solvent obtained by mixing.

  In order to facilitate handling during use or to prevent polymerization during storage, stabilizers may be added to the compounds or compositions 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 compound or composition of the present invention is 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. Can be applied by a method of developing a thin film and removing the solvent.

  If the substrate surface is subjected to an alignment treatment before coating, the compound or composition of the present invention can be aligned on the substrate. The treatment method is, for example, a method of forming a thin film made of polyimide, polyamide, polyvinyl alcohol or the like and rubbing it with a rayon cloth or the like, a method of obliquely depositing silicon oxide, a stretched film, a photo-alignment film or an ion. This is rubbing-free orientation using a 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 compound or composition of the present invention can be fixed by irradiation with electromagnetic waves. The wavelength of the electromagnetic wave is preferably 300 nm or more, and particularly preferably 365 nm. The temperature at the time of irradiation is a temperature at which the compound or composition is in a liquid crystal state, but is preferably 100 ° C. or lower to prevent thermal polymerization. An optical element having a helical pitch selectively reflects right or left circularly polarized light. When the wavelength of the reflected light is 350 to 750 nm, the circularly polarized light in the incident visible light region is selectively reflected. When the wavelength of the reflected light is 100 to 350 nm, light in the visible light region incident from the front is transmitted, so that it can be used as a negative c-plate. That is, when this optical element is sandwiched between two polarizing plates made of crossed Nicols, light cannot be transmitted in the front direction, but light is transmitted in an oblique direction. Since the wavelength of the reflected light is equal to the product of the refractive index of the optical element and the helical pitch, it is possible to arbitrarily optimize the wavelength of the selectively reflected light by adjusting the refractive index of the optical element and the helical pitch. Is possible.

  The composition of the present invention containing an optically active compound exhibits a helical structure on the substrate. If the composition is polymerized, a molded article having twist orientation can be produced. In the case of light having a wavelength (λ) that satisfies the expression “λ = refractive index × spiral pitch”, this molded body has a circularly polarized light separation function. 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. When producing a negative c-plate, the wavelength of the selectively reflected light needs to be less than 350 nm. Therefore, the helical pitch is preferably less than 200 nm. If it is less than 200 nm, a negative c-plate is obtained in any case, but in order to obtain a shorter helical pitch, it is necessary to mix a larger amount of binaphthalene derivative. In consideration of maintaining the temperature range of the liquid crystal phase, it is preferable that the addition amount of the binaphthalene derivative is small. Therefore, a preferable helical pitch is 1 nm or more and less than 200 nm, more preferably 10 nm or more and less than 200 nm, still more preferably 50 nm or more and less than 200 nm, particularly preferably 50 nm or more and less than 150 nm.

  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. A preferable optical anisotropy value is 0.05 to 50 μm, a more preferable optical anisotropy value is 0.1 to 20 μm, and a further preferable optical anisotropy value is 0.5 to 1 μm. A preferable retardation value is 0.05 to 50 μm, a more preferable retardation value is 0.1 to 20 μm, and a more preferable retardation value is 0.5 to 10 μm. A preferred haze value of the molded body is 1.5% or less, and a more preferred haze value is 1.0% or less. A preferable transmittance in the visible light region of the molded body is 80% or more, and a more preferable transmittance is 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, ornaments, 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 monofunctional compound or a composition mainly composed thereof. These preferred weight average molecular weights are 500 to 1,000,000, more preferred weight average molecular weights are 1,000 to 500,000, and particularly preferred weight average molecular weights are 5,000 to 100,000.

  The polymer of the present invention having thermosetting properties can be used for a polarizing plate, an optical compensator, a brightness enhancement film, a negative c-plate and the like for a liquid crystal display element. These are polymers having a three-dimensional network structure, and can be obtained as a polymer having a high degree of polymerization by polymerizing a polyfunctional compound or a composition mainly composed thereof. 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.

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. For example, the indication “C 100.0 Ch” indicates that the phase transition temperature from the crystal to the cholesteric phase is 100.0 ° C. HTP was calculated from the formula [HTP = p ⁻¹ × c ⁻¹ ] by measuring the pitch of a cholesteric liquid crystal composition obtained by mixing compound (1) with mother liquid crystal ZLI-1132 at 25 ° C. Here, c is% by weight of the compound (1), and p is pitch (μm).
The adhesion of the obtained polymer was examined by a cello tape (registered trademark) peel test. The cellotape (registered trademark) peel test was evaluated based on the test method of JIS standard “JIS-5400”, that is, the remaining mesh in 100 mm. In the following, liter, which is a unit of capacity, is denoted by the symbol L.

(R) -2,2′-bis [4- [4- [6- (3-ethyloxetane-3-ylmethyloxy) hexyloxy] benzoyloxy] benzoyloxy] -1,1′-binaphthalene [formula ( In 1-2), L ¹ is hydrogen, X linked to the 1,1′-binaphthalene ring is —OCO—, Z is —OCO—, and X linked to the polymerizable group is —O (CH ₂ ) ₆ OCH _2. -, A compound in which W is ethyl]

(R) -2,2′-dihydroxy-1,1′-binaphthalene (10 g, 34.9 mmol), 4-benzyloxybenzoic acid (23.9 g, 105 mmol), dicyclohexylcarbodiimide (21.7 g, 105 mmol), 4 A mixture of dimethylaminopyridine (12.8 g, 105 mmol) and dichloromethane (300 mL) was stirred at room temperature for 2 hours. The precipitated insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was purified by column chromatography (silica gel: 700 mL, eluent: toluene), and 17.1 g (yield 69%) of (R) -2,2′-bis (4-benzyloxybenzoyloxy) -1 , 1′-Binaphthalene was obtained as colorless crystals. ¹ H- and ¹³ C-NMR well supported the structure. Rf = 0.42.

(R) -2,2′-bis (4-benzyloxybenzoyloxy) -1,1′-binaphthalene (17 g, 24.1 mmol), 5% PdC (10 g), ethanol / toluene (300 mL / 300 mL) mixture Was stirred under a hydrogen atmosphere for 3 hours. The catalyst was removed by filtration, and the filtrate was concentrated. The residue was purified by column chromatography (silica gel: 2 L, eluent: toluene / ethyl acetate (1/1)), and 13.8 g (99% yield) of (R) -2,2′-bis (4 -Hydroxybenzoyloxy) -1,1'-binaphthalene was obtained as colorless crystals. ¹ H- and ¹³ C-NMR well supported the structure. Rf = 0.60.

  (R) -2,2′-bis (4-hydroxybenzoyloxy) -1,1′-binaphthalene (5.0 mg, 9.5 mL), 4- [6- (3-ethyloxetane-3-ylmethyloxy) ) Hexyloxy] benzoic acid (7.7 mg, 22.8 mmol), dicyclohexylcarbodiimide (4.7 g, 22.8 mmol), 4-dimethylaminopyridine (0.7 mg, 5.7 mmol) and dichloromethane (100 mL). Stir at room temperature for 2 hours. The precipitated insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was purified by column chromatography (silica gel: 1 L, eluent: ethyl acetate / toluene (3/7)), and 7.3 g (yield 58%) of (R) -2,2′-bis [4 -[4- [6- (3-Ethyloxetane-3-ylmethyloxy) hexyloxy] benzoyloxy] benzoyloxy-1,1'-binalene was obtained as a colorless viscous oil. 1H- and 13C-NMR well supported the structure. Rf = 0.65.

(R) -2,2′-bis [4- [4- [6- (3-ethyloxetane-3-ylmethyloxy) hexyloxy] benzoyloxy] -1,1′-biphenyl-4′-carbonyloxy ] -1,1′-binaphthalene [In the formula (1-8), L ¹ is hydrogen, X linked to the 1,1′-binaphthalene ring is —OCO—, the left Z is a single bond, and the right Z is − OCO-, X is _-O be linked to the polymerizable group _{(CH 2) 6 OCH 2 -} , the compound W is ethyl synthesis of

  Instead of 4-benzyloxybenzoic acid, 4-benzyloxy-1,1′-biphenyl-4′-carboxylic acid was used, and (R) -2,2′-bis [4] was prepared in the same manner as in Example 1. -[4- [6- (3-Ethyloxetane-3-ylmethyloxy) hexyloxy] benzoyloxy] -1,1′-biphenyl-4′-carbonyloxy] -1,1′-binaphthalene is a colorless amorphous solid Got as.

(S) -6,6′-Dibromo-2,2′-bis [4- [4- (2-oxiranylethoxy) benzoyloxy] -1,1′-biphenyl-4′-carbonyloxy] -1 , 1′-Binaphthalene [Compound wherein L ¹ is bromine, x is 2 and W is hydrogen in the formula (1-9c)]

Instead of (R) -2,2′-dihydroxy-1,1′-binaphthalene, (S) -6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthalene is replaced with 4- [6 (S) -6 in the same manner as in Example 1 except that 4- (2-oxiranylethoxy) benzoic acid was used instead of-(3-ethyloxetane-3-ylmethyloxy) hexyloxy] benzoic acid. , 6′-Dibromo-2,2′-bis [4- [4- (2-oxiranylethoxy) benzoyloxy] -1,1′-biphenyl-4′-carbonyloxy] -1,1′-binaphthalene Was obtained as colorless crystals.

(R) -6,6′-bis [6- [4- (4-pentylcyclohexyl) phenyloxy] hexyl] -2,2′-bis [4- [4- [6- (3-ethyloxetane-3] -Ylmethyloxy) hexyloxy] benzoyloxy] benzoyloxy] -1,1'-binaphthalene [in the formula (1), Q ¹ and Q ² are both 6- [4- (4-pentylcyclohexyl) phenyloxy] hexyl , Q ³ and Q ⁴ are both the formula (2), the left X is —OCO—, n is 1, A is 1,4-phenylene, Z is —OCO—, and —X—P is 6- [Synthesis of a compound that is 3-ethyloxetane-3-ylmethyloxy] hexyloxy]

  (R) -6,6′-bis [6- [4- (4-pentylcyclohexyl) phenyloxy] hexyl] -2, instead of (R) -2,2′-dihydroxy-1,1′-binaphthalene (R) -6,6′-bis [6- [4- (4-pentylcyclohexyl) phenyloxy] hexyl was prepared in the same manner as in Example 1 using 2′-dihydroxy-1,1′-binaphthalene. ] -2,2′-bis [4- [4- [6- (3-ethyloxetane-3-ylmethyloxy) hexyloxy] benzoyloxy] benzoyloxy] -1,1′-binaphthalene was synthesized. (R) -6,6′-bis [6- [4- (4-pentylcyclohexyl) phenyloxy] hexyl] -2,2′-dihydroxy-1,1′-binaphthalene is obtained from Mol. Cryst. Liq. Cryst , 2001, 364, 825.

  Preparation of photopolymerizable liquid crystal composition (Mix-1) and production of optical thin film

  Liquid crystal composition comprising the compound obtained in Example 2 (hereinafter referred to as compound (Ex-2)) [10 parts by weight], compound (A) [45 parts by weight] and compound (B) [45 parts by weight] (Mix-1) was prepared. Compounds (A) and (B) were synthesized according to the method of Japanese Patent Application No. 2003-203629, Macromolecules, 1993, 26 (6), 244, respectively.

  A polymerizable liquid crystal composition and a polymerization initiator are prepared by adding a cyclopentanone / toluene (1: 2) mixed solvent (3.0 g) and DTS-102 (10 mg) to the composition (Mix-1) [1.0 g]. The solution prepared to have a ratio of about 98 parts by weight: 2 parts by weight was applied to a saponified triacetyl cellulose film whose surface was rubbed with a rayon cloth using a spin coater (2000 rpm). The liquid crystal phase was aligned by leaving the solution on a hot plate at 70 ° C. for 3 minutes to remove the solvent. The temperature was returned to room temperature, and ultraviolet rays were irradiated for 30 seconds with a high-pressure mercury lamp (120 W / cm) to obtain a colorless and transparent optical thin film. When the spectrum of transmitted light was measured for the obtained optical thin film, there was no selective reflection of 350 nm or more. When effective retardation at 550 nm was measured, it was 0 nm in the case of normal incidence, and −35 nm in the case where the angle was inclined by 40 ° from the normal of the layer surface, confirming that it was a negative c-plate. The obtained optical film had a retardation change rate of less than 3% in a heat resistance test (100 ° C., 1000 hours). When the adhesion test was conducted, the number of remaining cells was 100, which was a favorable result.

Preparation of photopolymerizable liquid crystal composition (Mix-2) and production of optical thin film Compound (Ex-2) [5 parts by weight], compound (A) [47.5 parts by weight] and compound (B) of Example 2 A liquid crystal composition (Mix-2) consisting of [47.5 parts by weight] was prepared.

  A polymerizable liquid crystal composition and a polymerization initiator are prepared by adding a cyclopentanone / toluene (1: 2) mixed solvent (3.0 g) and DTS-102 (30 mg) to the composition (Mix-2) [1.0 g]. The solution prepared to have a ratio of 97 parts by weight: 3 parts by weight was applied to a saponified triacetyl cellulose film whose surface was rubbed with a rayon cloth using a spin coater (2000 rpm). The liquid crystal phase was aligned by leaving the solution on a hot plate at 70 ° C. for 3 minutes to remove the solvent. It returned to room temperature, and irradiated with the ultraviolet-ray for 30 second with the high pressure mercury lamp (120 W / cm), and obtained the optical thin film. This showed blue selective reflection.

  Preparation of photopolymerizable liquid crystal composition (Mix-3) and production of optical thin film

Compound (1-23a ′) [in the formula (1-23a), compounds in which L ¹ are both hydrogen: 10 parts by weight], compound (C) [60 parts by weight] and compound (D) [20 parts by weight] A liquid crystal composition (Mix-3) was prepared. Compounds (C) and (D) were synthesized according to the methods of Japanese Patent Application No. 2002-317433 and JP-A 61-064493, respectively.

  A colorless and transparent optical thin film was obtained in the same manner as in Example 6 except that the composition (Mix-3) was used instead of the composition (Mix-2). When the spectrum of transmitted light was measured for the obtained optical thin film, there was no selective reflection of 350 nm or more. Moreover, when the effective retardation at 550 nm was measured, it was 0 nm in the case of normal incidence, and −25 nm in the case where the angle was inclined by 40 ° from the normal of the layer surface, confirming that it was a negative c-plate.

  Preparation of photopolymerizable liquid crystal composition (Mix-4) and production of optical thin film

Example 7 using Compound (1-29a ′) [Compound of Formula (1-29a) wherein L ¹ is both hydrogen; 15% by weight] instead of Compound (1-23a ′) [10% by weight] A colorless and transparent optical thin film was obtained by the same method. When the transmission spectrum was measured about the obtained optical thin film, there was no selective reflection of 350 nm or more. When effective retardation at 550 nm was measured, it was 0 nm in the case of normal incidence, and −27 nm in the case where the angle was inclined by 40 ° from the normal of the layer surface, confirming that it was a negative c-plate.

  Preparation of photopolymerizable liquid crystal composition (Mix-5) and production of optical thin film

  In Example 5, a liquid crystal composition (Mix-5) was prepared using Compound (E) [45 parts by weight] instead of Compound (A). Compound (E) was synthesized according to the method of Japanese Patent Application No. 2003-203629. A polymerizable liquid crystal composition and a polymerization initiator are prepared by adding a cyclopentanone / toluene (1: 2) mixed solvent (3.0 g) and DTS-102 (20 mg) to the composition (Mix-5) [1.0 g]. The solution prepared so that the ratio of the ratio was approximately 98 parts by weight: 2 parts by weight was applied to a saponified triacetyl cellulose film whose surface was rubbed with a rayon cloth using a spin coater (2000 rpm). The liquid crystal phase was aligned by leaving the solution on a hot plate at 70 ° C. for 3 minutes to remove the solvent. The temperature was returned to room temperature, and ultraviolet rays were irradiated for 30 seconds with a high-pressure mercury lamp (120 W / cm) to obtain a colorless and transparent optical thin film. When the spectrum of transmitted light was measured for the obtained optical thin film, there was no selective reflection of 350 nm or more. Also, when the effective retardation at 550 nm is measured, the optical thin film obtained becomes 0 nm in the case of normal incidence and −36 nm in the case where the angle is inclined by 40 ° from the normal of the layer surface, and it is confirmed that it is a negative c-plate. confirmed.

Claims (24)

The compound represented by Formula (1).

In formula (1), Q ^{1 to} Q ⁴ are independently formula (2), hydrogen or halogen, and at least two of Q ^{1 to} Q ⁴ may represent different groups, respectively. In formula (2), A is independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6-diyl, and Any hydrogen in the ring may be replaced by halogen; X is independently a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene is replaced by —O—. may be; Z is a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CHCOO -, - OCOCH = CH -, - C≡CCOO -Or -OCOC ≡C—; n is 1 or 2, and a plurality of A may be the same group or different groups, and when n is 2, a plurality of Z are the same P may be any one of the polymerizable groups represented by formulas (P2), (P3) and (P8); and W may be Hydrogen or alkyl having 1 to 2 carbon atoms. However, when Q ¹ and Q ² are both hydrogen, and Q ³ and Q ⁴ are both formulas (2), P is not (P8). Q ^{1 to} Q ⁴ are independently the formula (2), hydrogen, fluorine, chlorine, or bromine; A is independently 1,4-cyclohexylene or 1,4-phenylene, and Any hydrogen in the ring may be replaced by halogen; X is independently a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene is replaced by —O—. is at best; Z is a single _{bond, -COO -, - OCO -,} - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CHCOO- or -OCOCH = CH- in which claim, 1. The compound according to 1. Q ^{1 to} Q ⁴ are independently formula (2), hydrogen, fluorine, chlorine, or bromine; A is independently 1,4-cyclohexylene, 1,4-phenylene, or any hydrogen Is 1,4-phenylene substituted with fluorine or chlorine; X is independently a single bond or alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene is —O— The compound according to claim 1, wherein Z is a single bond, —COO—, —OCO—, —CH═CHCOO—, or —OCOCH═CH—.   The compound according to claim 2 or 3, wherein in the formula (2) according to claim 1, P is a formula (P2) or (P3).   The compound according to claim 2 or 3, wherein P is formula (P2) in the formula (2) according to claim 1. The formula (2) in which Q ¹ and Q ² are independently halogen, and Q ³ and Q ⁴ may each represent different groups; P is the formula (P8) Compound. Q ¹ and Q ² are independently fluorine, chlorine or bromine, and Q ³ and Q ⁴ may each represent different groups; A is independently 1,4- Cyclohexylene or 1,4-phenylene, any hydrogen of these rings may be replaced by halogen; X is independently a single bond or alkylene of 1 to 10 carbons, Any of —CH ₂ — may be replaced by —O—; Z is a single bond, —COO—, —OCO—, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH; The compound according to claim 1, wherein = CHCOO- or -OCOCH = CH-; and P is the formula (P8). Q ¹ and Q ² are independently fluorine, chlorine or bromine, and Q ³ and Q ⁴ may each represent different groups; A is independently 1,4- Cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine or chlorine; X is independently a single bond or alkylene having 1 to 10 carbons, Any —CH ₂ — in the alkylene may be replaced by —O—; Z is a single bond, —COO—, —OCO—, —CH═CHCOO—, or —OCOCH═CH—; The compound according to claim 1, wherein P is the formula (P8). In the formula (1) according to claim 1, Q ^{1 to} Q ⁴ are each a formula (2) that may represent different groups; in the formula (2) according to claim 1, P is a formula (2) The compound according to any one of claims 1 to 3, which is P8).   A liquid crystal composition comprising at least two compounds, wherein at least one compound is the compound according to claim 1.   The liquid crystal composition according to claim 10, wherein all of the compounds are polymerizable compounds. In a proportion based on the total amount of the composition, at least one of the compounds according to any one of claims 1 to 9 is in the range of 0.01 to 90% by weight, each of the formulas (M1) and (M2) The liquid crystal composition according to claim 10 or 11, wherein at least one polymerizable compound selected from the group of compounds represented by formula (10) is in the range of 10 to 99.99% by weight.

In Formula (M1) and Formula (M2), P ¹ is independently any one of the polymerizable groups represented by Formulas (P9) to (P12); W is hydrogen, halogen, carbon R ¹ is hydrogen, fluorine, chlorine, —CN or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ -May be replaced by -O-, -COO- or -OCO-, and any hydrogen may be replaced by halogen; A ¹ 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, and these Any hydrogen in the ring is Androgenic, may be replaced by an alkyl halide of 1 to 3 alkyl carbon atoms or 1 to 3 carbon atoms; X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, in the alkylene Any —CH ₂ — may be replaced by —O—, —COO— or —OCO—; Z ¹ 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═CHCOO—, or —OCOCH═CH—; s is an integer of 1 to 3, and when s is 1, 2 or 3, the plurality of A ¹ may be the same group or different groups, and s is 2 or When Z is 3, a plurality of Z ¹ may each be the same group, Different groups may be used. At least one polymerizable compound selected from the group of compounds represented by formulas (M1) and (M2) is a compound represented by any one of formulas (M1a) to (M2c) The liquid crystal composition according to claim 12.

In formulas (M1a) to (M2c), P ¹ is any one of polymerizable groups represented by formulas (P9) to (P12); R ¹ is hydrogen, fluorine, chlorine, —CN , Or alkyl having 1 to 20 carbons, in which arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—, and optional hydrogen is replaced by halogen Ring A ² is independently 1,4-cyclohexylene or 1,4-phenylene, and W ¹ is independently hydrogen, halogen, C 1-3 alkyl or carbon X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —COO— or May be replaced by -OCO- p and q are independently 0 or 1, m is independently an integer of 0 to 5.   A polymer obtained by polymerizing at least one of the compounds according to claim 1.   The polymer obtained by polymerizing the composition of any one of Claims 10-13.   The polymer according to claim 14 or 15, which has a weight average molecular weight of 500 to 1,000,000.   The polymer according to claim 14 or 15, which has a weight average molecular weight of 1,000 to 500,000.   After aligning at least one of the compounds according to claim 1 or the liquid crystal composition according to any one of claims 10 to 13, a liquid crystal is obtained by polymerizing the compound or the composition by irradiation with electromagnetic waves. A molded article having optical anisotropy obtained by fixing the orientation state of the above.   The molded body according to claim 18, wherein the alignment state of the fixed liquid crystal is twist alignment.   An optical element comprising the molded article according to claim 18 or 19.   The optical element according to claim 20, having a helical pitch of 1 nm or more and less than 200 nm.   21. The optical element according to claim 20, wherein circular dichroism is exhibited for light having a wavelength in a part or all of a wavelength range of 350 to 750 nm.   The optical element according to claim 20, which exhibits circular dichroism in an ultraviolet region having a wavelength of 100 to 350 nm.   The polymer according to any one of claims 14 to 16, the molded article according to claim 18 or 19, and at least selected from the group of optical elements according to any one of claims 20 to 23. A liquid crystal display element containing one.