TW201608010A - Liquid crystal compound, liquid crystal composition, polymer and application thereof - Google Patents

Abstract

To provide a liquid crystal compound, a liquid crystal composition, a polymer and an optical anisotropy film, a polarizing plate and a display element capable of controlling refractive index anisotropy by a wavelength to exhibit low wavelength dispersion characteristics and also reverse wavelength dispersion properties, and to a liquid crystal composition containing the compound and having good coatability, or the like. A compound is represented by formula (1) below and a liquid crystal composition contains the compound.

Description

Liquid crystal compound, liquid crystal composition, polymer and application thereof

The present invention relates to a liquid crystalline compound having a benzothiophene, a benzofuran or an anthracene structure, a liquid crystal composition comprising the same, a polymer obtained from the liquid crystal composition, an optically anisotropic film, and Their use.

In recent years, a liquid crystal compound having a polymerizable group has been flexibly applied to an optically anisotropic film exhibiting birefringence (optical anisotropy) such as a reflective polarizer or a phase difference plate. The compound exhibits birefringence in a liquid crystal state, and its alignment is fixed by polymerization. The fixed alignment state of the polymer may be, for example, a homogeneous (horizontal alignment), a tilt (tilt alignment), a homeotropic (vertical alignment), and a twist (twist alignment).

An optically anisotropic film having parallel alignment can be used as a composite phase difference plate or a circularly polarizing plate by, for example, combining with a 1⁄2 wavelength plate, a 1⁄4 wavelength plate, or a film having other optical functions (refer to the patent document) 1).

The optical anisotropic film having a vertical alignment has a direction of the optical axis in the n _z direction, and a refractive index in the optical axis direction is larger than a refractive index in the direction orthogonal thereto, and thus is classified into a positive C-plate in the refractive index ellipsoid. . The positive C-plate can be applied to optical compensation of a horizontally aligned liquid crystal mode such as an In-Plane Switching (IPS) mode by combining with a film having other optical functions, such as a field of view of a polarizing plate. Improvement of angular characteristics (Non-Patent Document 1 to Non-Patent Document 3, Patent Document 2, and Patent Document 3).

The optical characteristics necessary for the optically anisotropic film vary depending on the use or purpose, and thus various liquid crystal compounds have been developed as the compound to be used. Further, since it is difficult to control the above-described anisotropy when it is alone, it is used in combination with a plurality of compounds to obtain a liquid crystal composition.

Such a liquid crystal composition is dissolved in an organic solvent for use as an ink for the purpose of adjusting coatability and the like. When a film having optical anisotropy is produced by using a liquid crystal composition, a liquid crystal compound, a photopolymerization initiator, a surfactant, or the like is dissolved in an organic solvent to prepare an adjusted ink such as a solution viscosity or a leveling property. The ink is applied onto the aligned substrate, and the solvent is dried to align the liquid crystal composition on the substrate. Then, it is irradiated with ultraviolet rays to be polymerized, and the alignment state is fixed. Usually, the organic solvent is dried and removed until polymerization is carried out at room temperature, and during this period, it is necessary to maintain a uniform liquid crystal state without crystallization or the like. Therefore, the polymerizable compound used in the liquid crystal composition must maintain good compatibility with other liquid crystal compounds or high solubility in an organic solvent, and further have a long-term liquid crystallinity near room temperature. Further, regarding the organic solvent, in consideration of an environmental load or an influence on the human body, it is required to have high solubility in an organic solvent having high safety.

Further, the polymer obtained from the liquid crystal composition requires high transparency, high mechanical strength, high adhesion to a substrate, low shrinkage, high heat resistance, and high in addition to optical anisotropy. Chemical resistance and other characteristics.

In the optically anisotropic layer formed of a rod-shaped molecule, generally, the two refractive indices ne of an anisotropic molecule (an abnormal refractive index in a direction parallel to the long axis of the molecule) and no (in a direction perpendicular to the long axis of the molecule) The usual refractive index decreases as the wavelength becomes larger. At this time, since no change in the refractive index of ne to the wavelength is large, the refractive index anisotropy (Δn=ne-no) decreases as the applied wavelength becomes larger. On the other hand, in a display device such as a liquid crystal display (LCD), the light source is white light containing light having a wavelength of about 380 nm to 800 nm, but is designed using a general optical anisotropic layer. When a 2λ or 1/4λ plate is used in combination, the above-mentioned wavelength dispersibility causes a problem that a change in a polarization state due to a wavelength occurs, and light becomes colored. In order to prevent this problem, it is necessary to control the wavelength dispersion in order to achieve a phase difference at each wavelength, and it is required to have a low dependence of refractive index anisotropy (low-wavelength dispersion characteristics) due to wavelength, or A material that becomes large and has an increased refractive index anisotropy (reverse wavelength dispersion property).

In order to obtain an optically anisotropic layer having a reverse wavelength dispersion property, a method of forming an angle by forming two retardation layers in the direction of refractive index anisotropy has been proposed (Patent Document 4 and Patent Document 5). However, such a laminate has the following problems: two retardation layers are required, an anisotropic angle of the two retardation layers is required, and the manufacturing complexity and optical anisotropy for forming the laminate are required. The film thickness of the layer is increased.

In order to solve the above problem, in order to solve the above problem, it is required to provide a liquid crystal compound having reverse wavelength dispersion characteristics without an optically anisotropic layer having a reverse wavelength dispersion under the condition of no layer buildup (Patent Documents 6 to 10).

However, since the compound described in Patent Document 6 has a low refractive index anisotropy, it is necessary to increase the film thickness in order to obtain a desired phase difference, and there is a concern that it is difficult to control the alignment uniformity because the aspect ratio is small. It is difficult to manufacture due to the long synthetic path. Since the compounds described in Patent Document 7 and Patent Document 8 have absorption in the visible region, it is likely to cause a decrease in transmittance or a color unevenness, and is not suitable for use in optical applications. The compounds described in Patent Document 9 and Patent Document 10 are relatively excellent in optical properties and manufacturing processes, but require further improvement in characteristics such as mechanical strength of the polymer, adhesion to the substrate, and heat resistance. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-372623 [Patent Document 2] International Publication No. 05/38517 A1 [Patent Document 3] US Patent Application Publication No. 2006/182900 (Patent Document 4) Japanese Patent Laid-Open [Patent Document 5] Japanese Patent Laid-Open Publication No. JP-A No. Hei. [Patent Document 9] Japanese Patent Laid-Open Publication No. 2005-289980 [Patent Document 10] Japanese Patent Laid-Open Publication No. 2010-031223 [Non-Patent Document]

[Non-Patent Document 1] MS Park et al., "Inverse Distance Weighting (IDW)" 2004 FMC8-4 [Non-Patent Document 2] M. Nakata et al., Society for Information Display (SID) 2006 P-58 [Non-Patent Document 3] KJ Kim et al., "Society for Information Display (SID)" 2006 Digest Page 1158-1161

[Problems to be solved by the invention]

The present invention resides in a low-wavelength dispersion characteristic capable of controlling refractive index anisotropy caused by a wavelength, and further exhibits reverse wavelength dispersion, and has good miscibility to other liquid crystal compounds and organic solvents. a compound; and a liquid crystal composition comprising the compound and exhibiting a good liquid crystal phase at a relatively low temperature and exhibiting good solubility in an organic solvent; and further using the liquid crystal composition to form excellent mechanical strength and heat resistance Polymer. [Technical means to solve the problem]

The inventors have conducted active research and found that a compound having a benzothiophene, a benzofuran or an anthracene structure can solve the above problems and complete the invention. That is, the present invention is as follows.

[1] a compound represented by the formula (1),

[Chemical 1] (In the formula (1), A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a pyridine-2,5-diyl group. Or naphthalene-2,6-diyl, of which at least one hydrogen may be via fluorine, chlorine, cyano, hydroxy, formamyl, trifluoroethenyl, difluoromethyl, trifluoromethyl, carbon The alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the alkyl ester having 1 to 5 carbon atoms or the alkyl fluorenyl group having 1 to 5 carbon atoms are substituted; and Z ¹ and Z ² are each independently a single Bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -OCH ₂ CH ₂ O-, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ - , -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N = N-, or -C≡C-; m and n are each independently an integer of 0 to 3, and is 1 ≦ m + n ≦ 4 relationship; X ¹ is -O -, - S- or -NR ³ - And R ³ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkyl anthracene group having 1 to 5 carbon atoms; Q ¹ is hydrogen, a halogen or a monovalent organic group; and R ¹ and R ² are each independently hydrogen and fluorine. Chlorine, trifluoro a group, a trifluoromethoxy group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl ester having 1 to 20 carbon atoms or a formula (2) the group represented;

[Chemical 2] In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or an alkylene group having 1 to 20 carbon atoms; At least one -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-; PG is a formula (PG-1) to (PG-8) a polymerizable group represented by either; * indicates a bonding site;

[Chemical 3] In the formulae (PG-1) to (PG-8), R ^{4 is} each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl). [2] The compound according to [1], wherein, in the formula (1), Q ¹ is a group represented by the formula (3) or the formula (4),

[Chemical 4] (In the formulas (3) and (4), Z ^{3 is} independently a single bond, -COO- or -COS-; Z ^{4 is} independently a single bond, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-; R ⁵ is hydrogen, fluorine, chlorine, cyano, carbon number 1-20 An alkyl group in which -CH ₂ - may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, wherein the hydrogen in the alkyl group may be substituted by halogen; A ^{3 is} independently a bivalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, and A ⁴ is a monovalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, A At least one hydrogen of the aromatic ring or the fused ring thereof in ³ and A ⁴ may be fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, carbon Alkoxy groups of 1 to 5, alkyl esters having 1 to 5 carbon atoms, alkyl alkane groups having 1 to 5 carbon atoms or thioalkyl groups having 1 to 5 carbon atoms; p is an integer of 0 to 2) .

[3] The compound according to [1] or [2], wherein, in the formula (1), at least one of R ¹ and R ² is a group represented by the formula (2). [4] The compound according to any one of [1] to [3] wherein, in the formula (1), X ¹ is -S-.

[5] The compound according to any one of [1] to [4] wherein, in the formula (1), A ¹ and A ² are each independently a 1,4-phenylene group or a 1,4-stretched ring. Hexyl, at least one of these groups may be a fluorine, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or a carbon number. 1 to 5 alkyl alkane groups are substituted; Z ¹ and Z ² are independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH= CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -.

[6] The compound according to any one of [1], wherein, in the formula (1), Q ¹ is a group represented by the formula (4), and in the formula (4), Z ⁴ is a single Key, p is an integer of 0 or 1. [7] The compound according to any one of [1] to [6] wherein, in the formula (1), at least one of A ¹ and A ² is a 1,4-cyclohexylene group.

[8] The compound according to any one of [1] to [7] wherein, in the formula (1), at least one of Z ¹ and Z ² is -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ - , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -.

[9] The compound according to any one of [1], wherein, in the formula (1), R ¹ and R ² are a group represented by the formula (2), and in the formula (2), PG The polymerizable group represented by the formula (PG-1), and R ⁴ is hydrogen or a methyl group.

[10] The compound according to any one of [1] to [9] wherein Q ¹ is a group represented by any one of the formulae (4-1) to (4-9),

[Chemical 5] (In the formula (4-1) to the formula (4-9), X ² is -O- or -S-, at least one -CH= may be substituted by -N=, at least one hydrogen may be subjected to fluorine, chlorine or cyano group. a trifluoroethenyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms. Substituted; * indicates the bonding site).

[11] A liquid crystal composition containing at least one of the compounds according to any one of [1] to [10]. [12] A liquid crystal composition containing at least one of the compounds according to any one of [1] to [10], and a compound group selected from the group consisting of the formula (M1) and the formula (M2) At least one,

[Chemical 6] (In the formula (M1) and (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, pyridine-2,5- Diyl, naphthalene-2,6-diyl, anthrone-2,7-diyl or anthracene-2,7-diyl, of which at least one hydrogen may be via fluorine, chlorine, cyano, hydroxyl, Mercapto group, trifluoroethylidene group, difluoromethyl group, trifluoromethyl group, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms or carbon Substituted with a 1-5 alkyl azide group; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO- , -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or - C≡C-; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, carbon number 1 to 20 alkoxy or alkyl 1-20 alkyl; q is an integer from 1 to 4; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-,- OCO- or -OCOO-).

[13] A liquid crystal composition containing at least one of the compounds according to any one of [1] to [10] and at least one of the compounds represented by formula (M1),

[Chemistry 7] (In the formula (M1), A ^{M is} independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and at least one of A ^M is a 1,4-cyclohexylene group, and at least one of these groups It may be fluorine, chlorine, trifluoroethenyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl ester having 1 to 5 carbon atoms. Or alkane groups having 1 to 5 carbon atoms; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ -; q is an integer of 1 or 2; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, carbon number 1-20 An alkyl group, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl ester having 1 to 20 carbon atoms; a is an integer of 0 to 20; R ^M is hydrogen or a methyl group, Y ^M It is a single bond, -O-, -COO-, -OCO- or -OCOO-).

[14] The liquid crystal composition according to any one of [11] to [13] which further contains at least one chiral compound. [15] The liquid crystal composition according to any one of [11] to [14] further comprising at least one dichroic dye compound. [16] A polymer obtained by irradiating ultraviolet light to the liquid crystal composition according to any one of [11] to [15]. [17] An optically anisotropic film, wherein the polymer according to [16] has optical anisotropy. [18] A polarizing plate comprising the optically anisotropic film according to [17]. [19] A display element comprising the optically anisotropic film according to [17]. [20] A display element comprising the polarizing plate according to [18]. [Effects of the Invention]

The compound represented by the formula (1) of the present invention is provided by separately or in combination with other known liquid crystal compounds or a plurality of compositions containing these liquid crystal compounds and uniformly aligned in an arbitrary form, thereby providing a reduction in refractive index of each material. The wavelength dependence of the opposite polarity or the material exhibiting the reverse wavelength dispersion as described. Further, the liquid crystal composition exhibits a good liquid crystal phase at a relatively low temperature and exhibits excellent properties such as good solubility in an organic solvent. In addition, the polymer obtained by polymerizing the liquid crystal composition of the present invention and the film containing the polymer are excellent not only in the effect of the wavelength dependency but also optical anisotropy, transparency, heat resistance, and adhesion. Excellent in dimensional stability and mechanical strength. Therefore, the polymer of the present invention is suitable for applications such as a retardation film, an optical compensation film, a polarizing element, a circularly polarizing element, an elliptically polarizing element, a color compensation film, and an angle of field compensation film.

The usage of the terms in this specification is as follows. First, the meaning of the term "liquid crystallinity" is not limited to having a liquid crystal phase. In other words, the liquid crystal compound is a general term for a compound having a liquid crystal phase and a compound which is not a liquid crystal phase but is useful as a component of the liquid crystal composition. The liquid crystal phase is a nematic phase, a dished phase, and a cholesteric alcohol, and in many cases is directed to the column phase. The liquid crystal lower limit temperature is a lower limit temperature at which the liquid crystal phase is displayed, and is a temperature at which the liquid crystal phase is converted into crystallization. Polymerizability refers to the ability to provide a polymer by single-body polymerization using methods such as light, heat, and catalyst. A liquid crystal compound having a polymerizable group in the liquid crystal compound is referred to as a polymerizable liquid crystal compound, and a polymerizable liquid crystal compound is sometimes contained in the liquid crystal compound. The polymerizable compound means a compound having a polymerizable group which does not exhibit liquid crystallinity. The case where a compound has a polymerizable group is sometimes referred to as a monofunctional or monofunctional compound. Further, when the compound has a plurality of polymerizable groups, it may be referred to as a polyfunctional or a name corresponding to the number of polymerizable groups. The compound represented by the formula (1) is sometimes expressed as the compound (1). The compound represented by the other formula is sometimes referred to by the same simplification method.

The term "at least one" used in the description of the structure of the compound means not only the position of at least one but also the number of at least one. For example, the expression "at least one A may be substituted by B, C or D" includes, in addition to the case where at least one A is substituted by B, at least one A is substituted by C, and at least one A is substituted by D, A case where a plurality of A are substituted by at least two of B to D. However, the definition in which at least one -CH ₂ - may be substituted by -O- does not include a substitution which results in a bond group -OO-. Further, in the case where at least one -CH ₂ - is substituted by -O-, there is no case where the carbon number exceeds the range described.

For example, Y ² in the formula (2) is an alkylene group having 1 to 20 carbon atoms, and at least one of -CH ₂ - in the alkylene group may be substituted by -O- or the like, but in this case, includes utilization The substituted alkyl group of -O- or the like does not have a carbon number of more than 20. This rule is the same for other definitions.

<<Compound>> The compound represented by the formula (1) is used for the purpose of controlling the wavelength dispersion of the refractive index anisotropy of the effect of the present invention. In this case, one type of the compound represented by the above formula (1) may be selected, or two or more types may be used.

The liquid crystalline compound usually has an aromatic ring or an alicyclic ring as a core skeleton, and has a rod-like or dish-shaped molecular shape in which a flexible group such as an alkyl group is bonded to the core skeleton. The compound of the present invention is a structure of the formula (1) having a benzothiophene, a benzofuran or an anthracene structure as the core skeleton.

[化8] In the formula (1), A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a pyridine-2,5-diyl group. Or naphthalene-2,6-diyl. Here, in the case where n and m are 2 or more, the A ¹ and A ² may be different in each of the repetitions. In order to impart high liquid crystallinity to the compound and have good miscibility with other liquid crystal compounds and organic solvents, A ¹ or A ^{2 is} independently preferably 1,4-phenylene or 1,4-extension. The cyclohexyl group is more preferably at least one of A ¹ or A ² is a 1,4-cyclohexylene group in order to lower the wavelength dispersibility of the refractive index anisotropy or vice versa. Further, in the 1,4-phenylene group and the 1,4-cyclohexylene group, at least one hydrogen may be through fluorine, chlorine, cyano group, hydroxyl group, formyl group, trifluoroethenyl group, difluoromethyl group, or A fluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylhydrazine group having 1 to 5 carbon atoms are substituted. However, in order to impart high liquid crystallinity to a compound and to produce a compound inexpensively, the hydrogen substituent is particularly preferably fluorine, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. An oxy group, an alkyl ester having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms.

Formula (1), Z ¹ or Z ² are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - COS -, - SCO -, - OCOO -, - CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -OCH ₂ CH ₂ O-, -CH=CHCOO-, -OCOCH=CH -, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-. Here, in the case where n and m are 2 or more, the Z ¹ and Z ² may be different in each of the repetitions. In order to impart high liquid crystallinity to the compound, it has good miscibility with other liquid crystal compounds and an organic solvent, and the compound is produced at low cost. Z ¹ and Z ² are each independently preferably a single bond, -OCH ₂ -, - CH ₂ O-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -. Further, in view of low transparency and good miscibility with other liquid crystal compounds and organic solvents, it is particularly preferred that at least one of Z ¹ and Z ² is -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ - , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -.

Further, in order to improve the liquid crystallinity of the compound of the formula (1), it has good miscibility with other liquid crystal compounds and an organic solvent, and m and n are each preferably an integer of 0 to 3, and 1 ≦ m + n ≦ 4 .

In the formula (1), X ¹ is -O-, -S- or -NR ³ -, and R ³ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. In order to have good miscibility with other liquid crystal compounds and an organic solvent, the wavelength dispersibility of refractive index anisotropy is lowered or vice versa, and X ^{1 is} preferably -S-.

In the formula (1), R ¹ and R ² are each independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms. An alkoxy group having 1 to 20 carbon atoms, an alkyl ester having 1 to 20 carbon atoms or a group represented by the formula (2).

[Chemistry 9] In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or an alkylene group having a carbon number of 1 to 20, the alkylene group Any of -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-; PG is of formula (PG-1) to formula (PG-8) A polymerizable group represented by either of them. * indicates the bonding site.

[化10] In the formulae (PG-1) to (PG-8), R ^{4 is} each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl.

With respect to the group represented by R ¹ or R ² , in the case where the present technique is applied to a film, at least one of R ¹ or R ² is preferably a group represented by the formula (2). Among them, the selection of the polymerizable group represented by the formula (PG-1) to the formula (PG-8) can be appropriately selected depending on the production conditions of the film. However, when a film is produced by photocuring which is generally used, it is preferably a selective formula (PG- in terms of high hardenability, solubility in a solvent, low crystallinity, and difficulty in occurrence of alignment defects. 1) An acrylic or methacrylic group represented.

Q ¹ of the compound represented by the formula (1) of the present invention is hydrogen, halogen or a monovalent organic group, and among them, a group represented by the formula (3) or the formula (4) is preferred.

[11] (In the formulae (3) and (4), Z ^{3 is} independently a single bond, -COO- or -COS-; Z ^{4 is} independently a single bond, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-; R ⁵ is hydrogen, fluorine, chlorine, cyano, carbon number 1-20 An alkyl group in which -CH ₂ - may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, wherein the hydrogen in the alkyl group may be substituted by halogen; A ^{3 is} independently a bivalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, and A ⁴ is a monovalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, A At least one hydrogen of the aromatic ring or the fused ring thereof in ³ and A ⁴ may be, fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, carbon The alkoxy group having 1 to 5 carbon atoms, the alkyl ester having 1 to 5 carbon atoms, the alkanoyl group having 1 to 5 carbon atoms or the thioalkyl group having 1 to 5 carbon atoms is substituted; and p is an integer of 0 to 2.

In the group represented by the above-mentioned Q ¹ , in order to reduce the wavelength dispersibility of the refractive index anisotropy or vice versa, it is more preferable that the group represented by the formula (4) is imparted to the compound in order to impart high liquid crystallinity to the compound. The Q ^{1 is} particularly preferably selected from the group represented by the formula (4-1) to the formula (4-9).

[化12] In the formulae (4-1) to (4-9), X ² is -O- or -S-, at least one -CH= may be substituted by -N=, and at least one hydrogen may be subjected to fluorine, chlorine, cyano, a trifluoroethenyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms Replace. * indicates the bonding site.

Among the compounds represented by the formula (1), the liquid crystallinity is excellent, the clearing point is low, the solubility in an organic solvent is high, and the compatibility with other compounds is high. Formula (1-1-1) to Formula (1-1-21), Formula (1-2-1) to Formula (1-2-6), or Formula (1-3-1) to Formula (1- 3-5) The structure represented.

[Chemistry 13]

[Chemistry 14]

[化15]

[Chemistry 16]

[化17]

[化18] In the formulae (1-1-1) to (1-3-5), R ¹ and R ² are each independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, and carbon number. An alkyl group of 1 to 20, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl ester having 1 to 20 carbon atoms, or a group represented by the formula (2).

[Chemistry 19] In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or an alkylene group having a carbon number of 1 to 20, the alkylene group At least one of -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-; PG is of formula (PG-1) to formula (PG-8) A polymerizable group represented by either of them.

[Chemistry 20] In the formulae (PG-1) to (PG-8), R ^{4 is} each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl. R ³ is hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkanoyl group having 1 to 5 carbon atoms, and R ⁵ is hydrogen, fluorine, chlorine, a cyano group or an alkyl group having 1 to 20 carbon atoms. CH ₂ - may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, in which the hydrogen may be replaced by a halogen, and R ⁶ is hydrogen, fluorine, chlorine , cyano group, nitro group, trifluoromethyl group, trifluoromethoxy group, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms, carbon number 1 An alkyl group of ～5 or a thioalkyl group having 1 to 5 carbon atoms.

The compound represented by the formula (1) of the present invention can be synthesized by combining a known method of organic synthetic chemistry. The method of introducing a target terminal group, a ring and a bonding group into a starting material is described in "Houben-Weyl" (Methods of Organic Chemistry, George-Tim Press (Georg) Thieme Verlag), Stuttgart, Organic Syntheses (John Wily & Sons, Inc.), Organic Reactions, John Wiley & Sons Publishing Company "Comprehensive Organic Synthesis" (Pergamon Press) and the new experimental chemistry lecture (Maruzen) are included in the book. Further, the structure of the synthesized compound can be confirmed, for example, by proton nuclear magnetic resonance (NMR) spectroscopy.

<<Liquid Crystal Composition>> The liquid crystal composition of the present invention contains at least one compound selected from the group consisting of the compounds represented by the formula (1). The liquid crystal composition of the present invention has a liquid crystal phase of a nematic phase or a dish phase at a relatively low temperature. When the liquid crystal composition of the present invention is applied onto a plastic substrate subjected to an alignment treatment such as rubbing treatment or a support substrate made of a plastic film-coated surface, it is formed into a parallel alignment or a mixed alignment. In addition, when a non-polymerizable or polymerizable optically active compound to be described later is added to the liquid crystal composition of the present invention, it is a torsional alignment. When a compound having a cardo structure or a monofunctional liquid crystal compound to be described later is added to the liquid crystal composition of the present invention, vertical alignment is easily obtained.

The constituent component other than the compound (1) may contain other liquid crystal compounds (excluding the polymerizable liquid crystal compound), other polymerizable liquid crystal compounds, surfactants, and other polymerizable properties insofar as the effects of the present invention are not impaired. a compound (excluding a polymerizable liquid crystal compound), a polymerization initiator, a photosensitizer, a chain transfer agent, an antioxidant, an ultraviolet absorber, a radical scavenger, a light stabilizer, an optically active compound, a decane coupling agent, and a solvent And other additives.

Other liquid crystal compounds can be selected from the compounds described in Liquid Crystal (LiqCryst, LCI Publisher GmbH, Hamburg, Germany) which is a database of liquid crystal compounds. Among them, a compound represented by the following formula (LC) is preferred.

[Chem. 21] In the formula (LC), A ^{5 is} independently any one selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl and naphthalene-2,6-diyl. a divalent group, wherein at least one hydrogen of the divalent group may be fluorine, chlorine, cyano, hydroxy, decyl, trifluoroethyl, difluoromethyl, trifluoromethyl, carbon number 1-5 An alkyl group, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylhydrazine group having 1 to 5 carbon atoms; Z ^{5 is} independently a single bond or has a carbon number of 1 to 20 The alkyl group, at least one of -CH ₂ - may be via -O-, -CO-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C - substituted, at least one hydrogen may be substituted by halogen; b is an integer from 1 to 5; and R ^{8 is} independently hydrogen, fluorine, chlorine, cyano, hydroxy, decyl, trifluoroethenyl, difluoro A methyl group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of -CH ₂ - in the alkyl group may be substituted by -CH=CH-.

Specific examples of the compound represented by the formula (LC) are shown below.

[化22]

[化23]

[Chem. 24] 100% by weight of the total amount of at least one selected from the group of compounds of the present invention represented by the formula (1) and at least one selected from the group of known compounds represented by the formula (LC), the present invention The liquid crystal composition preferably contains 1% by weight to 90% by weight of the compound of the present invention represented by the formula (1), and 10% by weight to 99% by weight of the compound represented by the formula (LC).

The other polymerizable liquid crystal compound is preferably a compound represented by the following formula (M1) and formula (M2).

[化25] In the formula (M1) and the formula (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, pyridine-2,5-di. a base, naphthalene-2,6-diyl or anthracene-2,7-diyl, of which at least one hydrogen may be via fluorine, chlorine, cyano, hydroxy, methylidene, trifluoroethylidene, a fluoromethyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylhydrazine group having 1 to 5 carbon atoms; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-; X ^M is hydrogen, fluorine a chlorine, a trifluoromethyl group, a trifluoromethoxy group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a carbon number of 1 to 20 Alkyl ester; q is an integer from 1 to 4; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO- .

Here, in the case where q is 2 or more, the A ^M and Z ^M may be different in each of the repetitions. Among the compounds represented by the formula (M1) and the formula (M2), a compound represented by the formula (M1) is more preferable, and in the formula (M1), a compound as follows: A ^{M is} independently 1,4-phenylene or 1,4-cyclohexylene, at least one of A ^M is 1,4-cyclohexylene, at least one of 1,4-phenylene or 1,4-cyclohexylene The hydrogen may be fluorine, chlorine, trifluoroethenyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. The ester or alkane group having 1 to 5 carbon atoms is substituted; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, - CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ -; q is an integer of 1 or 2; X ^M is hydrogen, fluoro, chloro, trifluoromethyl, trifluoromethoxy, cyano, having 1 to 20 carbon atoms, An alkyl group, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms; a is an integer of 0 to 20; R ^M is hydrogen or a methyl group; ^M is a single bond, -O-, -COO-, -OCO- or -OCOO-.

A compound represented by the following formula (M3) may also be included as another polymerizable liquid crystal compound.

[Chem. 26] In the formula (M3), A ^{M is} independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and at least one of these groups may be a fluorine, a chlorine, a cyano group, a hydroxyl group or a methyl group. a trifluoroethenyl group, a difluoromethyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or a carbon number of 1 to 5. Substituted by an alkano group of 5; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH -, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO- , -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C -; c and d are each an integer of 0 to 3, and are in the relationship of 1 ≦ m + n ≦ 4; a is an integer of 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O- , -COO-, -OCO- or -OCOO-. Here, in the case where c and d are 2 or more, the A ^M and Z ^M may be different in each of the repetitions.

The compound represented by the formula (M1) is a monofunctional polymerizable liquid crystal compound, and it is easy to control the liquid crystal temperature range, optical characteristics, and alignment property of the liquid crystal composition, and the compound having 1,4-cyclohexylene group in at least one of A ^M is more It is easy to control the wavelength dispersion characteristics or the temperature range of the liquid crystal phase, and the like. The compound represented by the formula (M2) is a difunctional polymerizable liquid crystal compound, and since the polymer has a three-dimensional structure, it is a hard polymer as compared with the compound represented by the formula (M1) having one polymerizable group. The compound represented by the formula (M3) is a trifunctional polymerizable liquid crystal compound which can further form a strong network and is a harder polymer than a compound having one or two polymerizable groups. Hereinafter, the compound represented by the formula (M1), the formula (M2), and the formula (M3) or the compound derived from these compounds may be referred to as the formula (M).

Preferred examples of the compound represented by the formula (M1) are shown below.

[化27]

[化28] In the formulae (M1-1) to (M1-23), R ^{M is} independently hydrogen or a methyl group, and a is independently an integer of from 1 to 12.

Hereinafter, preferred examples of the compound represented by the formula (M2) are shown.

[化29]

[化30]

[化31] In the formulae (M2-1) to (M2-31), R ^{M is} independently hydrogen or a methyl group, and a is independently an integer of from 1 to 12. When there are two or more a's in the formula, any two a's may be the same or different.

Preferred examples of the compound represented by the formula (M3) are shown below.

[化32]

[化33] In the formulae (M3-1) to (M3-10), R ^{M is} independently hydrogen or a methyl group, and a is independently an integer of from 1 to 12. When there are two or more a's in the formula, any two a's may be the same or different.

a total amount of 100 weights relative to at least one selected from the group of compounds of the present invention represented by formula (1) and at least one compound selected from the group consisting of compounds represented by formula (M1) and formula (M2) %, the polymerizable liquid crystal composition of the present invention preferably contains 10% by weight to 90% by weight of at least one selected from the group consisting of the compounds of the present invention represented by the formula (1). When the content of the respective components in the liquid crystal composition is within the above range, a liquid crystal composition which is easy to control the wavelength dispersion of refractive index anisotropy and has good coatability can be obtained, and further, can be remarkably expressed. The effect of the polymer of the present invention is obtained.

Further, the compound represented by the formula (LC) or the formula (M3) may be further contained. The liquid crystal composition of the present invention may further comprise a surfactant. The surfactant is preferably a nonionic surfactant, and when the nonionic surfactant is contained in the liquid crystal composition, it has an effect of improving the smoothness of the coating film containing the liquid crystal composition.

In terms of the weight ratio with respect to the weight of the compound represented by the formula (1), and in the case of containing other liquid crystal compound or other polymerizable liquid crystal compound, with respect to the compound represented by the formula (1) The weight ratio of the total weight is preferably 0.0001 to 0.5 in the case where a nonionic surfactant is added. A more preferred weight ratio ranges from 0.0001 to 0.005.

Examples of the nonionic surfactant include an anthrone-based nonionic surfactant, a fluorine-based nonionic surfactant, and a hydrocarbon-based nonionic surfactant. A commercially available product of an anthrone-based nonionic surfactant is, for example, a Polyflow ATF-produced by Kyoritsu Chemical Co., Ltd., which is an unmodified anthrone or a modified anthrone. 2, Glanol 100, Glanol 115, Glanol 400, Glanol 410, Glanol 435, Glanol 440, Glanol 450 , Glanol B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK- 331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK-3510, and BYK-3570.

Commercial products of the fluorine-based nonionic surfactant include, for example, BYK-340, Ftergent 251, Ftergent 221MH, Ftergent 250, FTX-215M, FTX- 218M, FTX-233M, FTX-245M, FTX-290M, FTX-209F, FTX-213F, Ftergent 222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, Ftergent 212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-720C, FTX-740C, FTX-207S, FTX-211S, FTX-220S, FTX- 230S, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L, KB-F2M, KB-F2S, KB-F3M, and KB-FaM.

A commercially available product of a hydrocarbon-based nonionic surfactant is, for example, Polyflow No. 3, Polyflow No. 50 EHF, and Peliver, which have an acrylic polymer as a main component. Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, Polyflow No. 95, Polyflow No. 99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK- 380N, BYK-381, BYK-392, and BYK-Silclean3700.

Further, any of the above-mentioned Polyflow and Glanol is the name of a product sold by Kyoritsu Chemical Co., Ltd. BYK is the name of a product sold by BYK-Chemie Japan. Ftergent, FTX and KB are the names of goods sold by Neos.

The surfactant may be used singly or in combination of two or more. Next, other polymerizable compounds, additives, and organic solvents are exemplified. These compounds are also commercially available.

Other polymerizable compounds include vinyl derivatives, styrene derivatives, (meth)acrylic acid derivatives, oxirane derivatives, oxetane derivatives, sorbic acid derivatives, and antibutene. A compound such as an acid derivative or an itaconic acid derivative which does not have liquid crystallinity. Among the other polymerizable compounds having no liquid crystallinity, there are a compound having one polymerizable group, a compound having two polymerizable groups, and a polyfunctional compound having three or more polymerizable groups.

Other polymerizable compounds may be added as long as the liquid crystal phase can be maintained. In terms of the weight ratio with respect to the weight of the compound represented by the formula (1), and in the case of containing other liquid crystal compound or other polymerizable liquid crystal compound, relative to the compound represented by the formula (1) The weight ratio in terms of the total weight is preferably 0.5 or less.

Examples of the compound having a polymerizable group include styrene, nucleoside-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, and fatty acid vinyl ester (for example). : vinyl acetate), α,β-ethylenically unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl (meth)acrylate a base ester (having an alkyl group having 1 to 18 carbon atoms), a hydroxyalkyl (meth)acrylate (carbon number of 1 to 18 of a hydroxyalkyl group), and an aminoalkyl (meth)acrylate (aminoalkyl) The number of carbon atoms of the group is 1 to 18), and the ether oxygen-containing alkyl ester of (meth)acrylic acid (the number of carbon atoms of the alkyl group containing an ether oxygen is 3 to 18, for example, methoxyethyl ester, ethoxyethyl ester, Methoxypropyl ester, 2-(2-methylethyl)ethyl ester, 2-(2-ethylethyl)ethyl ester, and 2-(2-butylethyl)ethyl ester), N-ethylene Ethylamine, p-tert-butyl benzoate, vinyl N,N-dimethylaminobenzoate, vinyl benzoate, trimethyl vinyl acetate, 2,2-dimethylbutyric acid Vinyl ester, vinyl 2,2-dimethylvalerate 2-methyl-2-butyric acid vinyl ester, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutyrate, dicyclopentyloxyethyl (meth)acrylate, Isobornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl myristyl (meth)acrylate, (meth)acrylic acid Dicyclopentyl ester, dicyclopentenyl (meth)acrylate, 2-propenyloxyethyl succinic acid, 2-propenyl methoxyethyl hexahydrophthalic acid, 2-acryloxy ethoxylate Phthalic acid, 2-propenyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloxyethyl acid phosphate, 2-methylpropenyloxy acid Mono(meth) acrylate or di(meth) acrylate of polyalkylene glycol such as ethyl ester and polyethylene glycol having a degree of polymerization of from 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide Or a polyalkylene glycol such as a polyethylene glycol having a polymerization degree of from 1 to 100, a polyalkylene glycol having a polymerization degree of from 1 to 100, and a copolymer of ethylene oxide and propylene oxide. Methyl) acrylate or the like.

Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and neopentane. Diol diacrylate, dimethylol tricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A ring Ethylene oxide (EO) addition diacrylate, bisphenol A glycidyl diacrylate (Viscoat V#700), polyethylene glycol diacrylate, and methyl groups of these compounds Acrylate compound, etc.

Examples of the compound having three or more polymerizable groups include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylol EO addition tri(meth)acrylate. , tris(methyl) propylene decyloxyethyl phosphate, tris((meth) propylene decyloxyethyl) isocyanurate, alkyl modified dipentaerythritol tri(meth) acrylate, EO Modified trimethylolpropane tri(meth)acrylate, propylene oxide (PO) modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl Modified dipentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkane The base-modified dipentaerythritol penta (meth) acrylate, Viscoat V#802 (functional group number = 8), Viscoat V#1000 (functional group number = average 14), and the like. "Viscoat" is the trade name of Osaka Organic Chemical Co., Ltd. The functional group is 16 or more by Boltorn H20 (16-functional) sold by Perstorp Specialty Chemicals, Boltorn H30 (32-functional), Bolto (Boltorn) H40 (64-functional) is used as a raw material, and they are obtained by propylene oximation.

Further, the polymerizable compound may, for example, be a polymerizable anthracene derivative having a cardo structure. These compounds are suitable for the control of the alignment direction or to further increase the degree of hardening of the polymer. Examples of the polymerizable anthracene derivative having a cardo structure are shown in the formula (α-1) to the formula (α-6).

[化34] Further, examples of the other polymerizable compound include a polymerizable compound having a bisphenol structure. These compounds are suitable for the aid of the film forming ability or alignment uniformity of the liquid crystal composition. Examples of the polymerizable bisphenol derivative are shown in the formula (N-1) to the formula (N-6).

[化35] These other polymerizable compounds may be used singly or in combination of two or more. Further, these compounds may also be commercially available.

In order to optimize the polymerization rate, a polymerization initiator may also be added to the liquid crystal composition. The polymerization initiator may, for example, be a photo radical initiator. The photoradical polymerization initiator may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2- Dimethoxy-1,2-diphenylethane-1-one (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Yan Irgacure 127, Irgacure 500 (a mixture of Irgacure 184 and benzophenone), Irgacure 2959, Irgacure 907, Yan Jiagu (Irgacure) 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure ) 1800, Irgacure 1850, Irgacure 1870, Darocure 4265, Darocure MBF, Darocure TPO, Irgacure 784, Yanjia Irgacure 754, Irgacure OXE01, Irgacure OXE02, and the like. Both Darocure and Irgacure are the names of products sold by BASF.

Further, the photoradical polymerization initiator may be exemplified by p-methoxyphenyl-2,4-bis(trichloromethyl)triazine and 2-(p-butoxystyryl)-5-trichloromethyl. Base-1,3,4-oxadiazole, 9-phenyl acridine, 9,10-benzophenazine, benzophenone/micilenone mixture, hexaarylbiimidazole/mercaptobenzimidazole mixture , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyldimethylketal, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 2,4-diethyloxaxanone/p-dimethylaminobenzoic acid methyl ester mixture, benzophenone/methyltriethanolamine mixture, etc. .

In terms of the weight ratio with respect to the weight of the compound represented by the formula (1), and in the case of containing other liquid crystal compound or other polymerizable liquid crystal compound, relative to the compound represented by the formula (1) The photoradical polymerization initiator is preferably added in an amount of from 0.0001 to 0.20 by weight based on the total weight. A more preferable range of the weight ratio is 0.001 to 0.15. A particularly preferred range is from 0.01 to 0.15. The photoradical initiator may be used singly or in combination of two or more. Further, these polymerization initiators may also be commercially available.

Further, a sensitizer may be added to these photoradical polymerization initiators for use. Examples of the sensitizer include isopropyl thioxanthone, diethyl thioxanthone, ethyl-4-dimethylamino benzoate (Darocure EDB), 2-ethyl group. Hexyl-4-dimethylaminobenzoic acid ester (Darocure EHA) and the like. These sensitizers may be used singly or in combination of two or more. Further, these sensitizers may also be commercially available.

In order to control the polymerization rate, mechanical properties, and the like of the polymer, a chain transfer agent may be added to the liquid crystal composition. By using a chain transfer agent, the reaction rate or chain length of the obtained polymer can be controlled. When the amount of the chain transfer agent is increased, the polymerization reaction rate is lowered and the length of the polymer chain is decreased. Preferred chain transfer agents are thiol compounds or styrene dimers. These chain transfer agents may be used singly or in combination of two or more. Further, these chain transfer agents may also be commercially available.

Examples of the thiol-based chain transfer agent include dodecyl mercaptan, 2-ethylhexyl-3-mercaptopropionate, etc. as a monofunctional thiol, or trimethylol as a polyfunctional thiol. Propane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyloxy)butane (Karenz MT BD1), pentaerythritol IV (3-mercaptobutyrate) (Karenz MT PE1), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione (Karenz MT NR1) and the like. "Karenz" is the trade name of Showa Denko Co., Ltd.

The styrene dimerization system chain transfer agent may, for example, be 2,4-diphenyl-4-methyl-1-pentene or 2,4-diphenyl-1-butene. In the liquid crystal composition, a polymerization inhibitor may be added in order to prevent polymerization from proceeding during storage. A known polymerization inhibitor can be used, and preferred examples thereof are: 2,5-di(t-butyl)hydroxytoluene (BHT), hydroquinone, methylene blue, a nitroso compound such as diphenyl picryl hydrazide (DPPH), phenothiazine, N,N-dimethyl-4-nitrosoaniline, o-hydroxybenzophenone, and 2H-1 a benzothiazine derivative such as 3-benzothiazin-2,4(3H)-dione.

In order to improve the preservability of the liquid crystal composition, a polymerization inhibitor may be added. In the case where a radical is generated in the liquid crystal composition or the liquid crystal composition solution, the polymerization reaction of the polymerizable compound is promoted. For the purpose of preventing the polymerization reaction, a polymerization inhibitor is preferably added. A phenolic antioxidant, a sulfur-based antioxidant, and a phosphate-based antioxidant can be used as a polymerization inhibitor.

In order to further improve the weather resistance of the liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, or the like may be added. Examples of the ultraviolet absorber include: Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Emperor Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Emperor Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Di Nubin (Tinuvin) 479, Tinuvin 5236, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Ai Adekastab LA-31, Adekastab 1413, and Adekastab LA-51. "Tinuvin" is the trade name of BASF (Japan), and "Adekastab" is the trade name of ADEKA. These ultraviolet absorbers may be used singly or in combination of two or more. Further, these ultraviolet absorbers may also be commercially available.

Examples of the light stabilizers include: Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, and Di Nubin (Tinuvin) 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, Tinuvin 5060, Tinuvin 5151, Chimassorb 119FL, Chimassorb 944FL, Chimassorb 944LD, Eddie Costa Adekastab LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Eddie Costab Adekastab) LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, Adekastab LA-87, Cyasorb UV-3346 manufactured by Cytec, and Goodri Ch) The company's Goodrite UV-3034 and so on. "Chimassorb" is the trade name of BASF (shares). These light stabilizers may be used singly or in combination of two or more. Further, these light stabilizers may also be commercially available.

Examples of the antioxidant include: Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 of ADEKA, by Sumitomo Chemical Co., Ltd. ) sold by Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80, as well as by Essence sold by BASF. Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245, and the like. These antioxidants may be used singly or in combination of two or more. Further, these antioxidants may also be commercially available.

A decane coupling agent may be added to the liquid crystal composition in order to control adhesion to the substrate or the like. Examples of the decane coupling agent include vinyl trialkoxy decane, 3-isocyanate propyl triethoxy decane, and N-(2-aminoethyl) 3-aminopropyl trialkoxy decane. N-(1,3-dimethylbutylene)-3-(trialkoxyalkyl)-1-propanamine, 3-glycidoxypropyltrialkoxydecane, 3-chlorotrioxane Oxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrialkoxydecane, and the like. Further, among the alkoxydecanes, a dialkoxymethyl decane obtained by substituting one of the alkoxy groups (three) with a methyl group can also be used as a decane coupling agent. These decane coupling agents may be used singly or in combination of two or more. Further, these decane coupling agents may also be commercially available.

In order to facilitate coating, the liquid crystal composition of the present invention may be prepared by diluting a liquid crystal composition with a solvent or dissolving each component of the liquid crystal composition in a solvent to prepare a liquid crystal composition containing a liquid crystal composition and a solvent. Solution. Examples of the solvent include an ester solvent, a guanamine solvent, an alcohol solvent, an ether solvent, a glycol monoalkyl ether solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent. A halogenated aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone solvent, an acetate solvent, or the like.

The ester solvent is preferably an alkyl acetate (eg methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, Amyl acetate and isoamyl acetate), ethyl trifluoroacetate, alkyl propionate (eg methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and propyl acetate) Butyl acrylate), alkyl butyrate (eg methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), dialkyl malonate (eg: Diethyl malonate), alkyl glycolate (eg methyl carboxylate and ethyl glycolate), alkyl lactate (eg methyl lactate, ethyl lactate, isopropyl lactate, N-propyl lactate, butyl lactate and ethylhexyl lactate), glycerol monoacetate, γ-butyrolactone, and γ-valerolactone.

The guanamine solvent is preferably: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N-methylpropionamide, N,N-dimethylformamide, N,N -diethylformamide, N,N-diethylacetamide, N,N-dimethylacetamide dimethyl acetal, N-methyl caprolactam, and dimethylimidazolidinone Wait.

The alcohol solvent is preferably methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, tert-butanol, second butanol, butanol, 2-ethylbutyl Alcohol, n-hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-pentanol, hexafluoro-2-propanol, C Triol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, and Cyclohexanol and the like.

The ether solvent is preferably ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis(2-propyl) ether, 1,4-dioxane, tetrahydrofuran (THF) or the like.

The diol monoalkyl ether solvent is preferably: ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, two Glycol monoethyl ether), triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (eg propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg dipropylene glycol monomethyl ether), ethylene glycol monoalkane Ethyl acetate (eg ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether acetate (eg diethylene glycol monoethyl ether acetate), triethylene glycol monoalkane Ethyl ether acetate, propylene glycol monoalkyl ether acetate (eg propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (Example: dipropylene glycol monomethyl ether acetate), and diethylene glycol methyl ether.

The aromatic hydrocarbon solvent is: benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, cumene, n-propylbenzene, tert-butylbenzene, and second butyl. Benzene, n-butylbenzene and tetrahydronaphthalene. A preferred example of the halogenated aromatic hydrocarbon solvent is chlorobenzene or the like. The aliphatic hydrocarbon solvent is preferably hexane or heptane. The halogenated aliphatic hydrocarbon solvent is preferably chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene or tetrachloroethylene. The alicyclic hydrocarbon solvent is preferably cyclohexane or decalin.

The ketone solvent is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone or methyl propyl ketone. The acetate solvent is preferably ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetonitrile acetate, and acetic acid-1-methoxy-2- Propyl ester and the like.

From the viewpoint of the solubility of the liquid crystal compound, a guanamine solvent, an aromatic hydrocarbon solvent, or a ketone solvent is preferably used. When considering the boiling point of the solvent, it is preferred to use an ester solvent or an alcohol solvent in combination. An ether solvent or a glycol monoalkyl ether solvent. The selection of the solvent is not particularly limited. When a plastic substrate is used as the support substrate, in order to prevent deformation of the substrate, it is necessary to lower the drying temperature and prevent the solvent from eroding the substrate. The solvent to be preferably used in this case is an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, an acetate solvent, or a glycol monoalkyl ether solvent.

The ratio of the solid content in the solution of the liquid crystal composition is from 5% by weight to 70% by weight based on the total weight of the solution. A preferred range of the ratio is from 10% by weight to 50% by weight, and a more preferred range is from 10% by weight to 40% by weight. These solvents may be used singly or in combination of two or more. These solvents are also commercially available.

In the following description, a polymer (optical anisotropic film) obtained by polymerizing a liquid crystal composition may be referred to as a liquid crystal film. The liquid crystal film can be obtained in the following manner. First, the liquid crystal composition is applied onto a support substrate in a fluid state to form a coating film. In the case of preparing a solution having a liquid crystal composition, it is applied onto a support substrate and dried to form a coating film. The coating film is irradiated with light to polymerize the liquid crystal composition, and the composition in the coating film is fixed in a nematic alignment formed by a liquid crystal state. The material of the support substrate that can be used includes glass, plastic, and the like. Plastics can be cited as: polyimine, polyamidimide, polyamine, polyether oximine, polyether ether ketone, polyether ketone, polyketone sulfide, polyether oxime, polyfluorene, polyphenylene sulfide Ether, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol , polypropylene, cellulose, triacetyl cellulose and some of its saponified materials, epoxy resins, phenol resins, and cyclic olefin resins. The support substrate is usually in the form of a sheet or a film.

The cycloolefin-based resin may, for example, be a norbornene-based resin or a dicyclopentadiene-based resin, but is not limited to these resins. Among these resins, those which do not have an unsaturated bond or are unsaturated are used. For example, a hydrogenated product of a ring-opening (co)polymer of one or two or more kinds of norbornene-based monomers, an addition (co)polymer of one or two or more kinds of norbornene-based monomers, and a descending product may be mentioned. Addition copolymer of borneol-based monomer and olefin-based monomer (α-olefin such as ethylene), norbornene-based monomer and cycloolefin-based monomer (cyclopentene, cyclooctene, 5,6-dihydrogen) Specific examples of the addition copolymer of dicyclopentadiene or the like, and modified products thereof include: ZEONEX and ZEONOR (all are trade names, Japan Rui) ZEON (manufactured by ZEON), ARTON (trade name, JSR (share) manufacturing), Topas (TOPAS) (trade name, manufactured by TICONA), Appel ( APEL) (trade name, manufactured by Mitsui Chemicals Co., Ltd.), Escena (trade name, manufactured by Sekisui Chemical Industry Co., Ltd.), OPTOREZ (trade name, manufactured by Hitachi Chemical Co., Ltd.) ).

The film (plastic film) containing these plastics which can be used as a support substrate may be a uniaxially stretched film or a biaxially stretched film. These films may be, for example, a film subjected to surface treatment such as hydrophilization treatment such as corona treatment or plasma treatment or hydrophobization treatment. The method of hydrophilization treatment is not particularly limited, and it is preferably corona treatment or plasma treatment, and a particularly preferable method is plasma treatment. For the plasma treatment, the method described in JP-A-2002-226616, JP-A-2002-121648, and the like can be used. Further, in order to improve the adhesion between the liquid crystal film and the plastic film, an adhesive undercoat layer may be formed. Such an adhesive undercoat layer is not limited to any one of an inorganic material and an organic material as long as it improves the adhesion between the liquid crystal film and the plastic film. In addition, the plastic film may also be a laminated film. Instead of a plastic film, a metal substrate such as aluminum, iron, or copper having a slit-like groove on the surface thereof, or a bismuth glass, a borosilicate glass, or a vermiculite glass which is etched into a slit shape may be used. Flint glass) and the like.

On the support substrate such as a glass substrate or a plastic film, when a liquid crystal film of parallel alignment and mixed alignment is formed before the coating film of the liquid crystal composition is formed, physical and mechanical surface treatment by friction or the like is performed. In the case of forming a liquid crystal film which is vertically aligned, there are many cases where surface treatment such as rubbing is not performed, but rubbing treatment can be performed in terms of preventing alignment defects and the like. Any method may be employed for the rubbing treatment, and a rubbing cloth containing a raw material such as rayon, cotton, polyamide or the like is wound around a metal roll or the like to make the roll in contact with the support substrate or the polymer film. A method of moving while rotating; a method of moving the support substrate side in a state where the roller is fixed. The rubbing treatment may be performed directly on the support substrate, or a polymer film such as polyimine which is generally called an alignment film may be provided in advance on the support substrate, and the polymer film may be subjected to a rubbing treatment. The method of rubbing treatment is as described above. Depending on the type of the supporting substrate, the yttrium oxide may be vapor-deposited on the surface thereof to impart an alignment ability.

Further, in the case of forming a parallel alignment and a mixed alignment liquid crystal film, in addition to performing physical and mechanical surface treatment by friction or the like, a polyimine which is generally called a photoalignment film may be previously provided on the support substrate. Or a polymer film such as a polyacrylate, and the polymer film is subjected to polarization UV treatment.

Examples of the coating method for obtaining a uniform film thickness when coating a liquid crystal composition or a solution thereof are: spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dip coating method, Spray coating method, meniscus coating method, and die coating method. In particular, a wire bar coating method or the like which applies shear stress to the liquid crystal composition at the time of coating can be used to control the alignment of the liquid crystal composition without performing surface treatment of the substrate by rubbing or the like.

When the solution of the liquid crystal composition of the present invention is applied, heat treatment may be performed in order to form a polymerizable liquid crystal layer having a uniform film thickness, that is, a layer of the liquid crystal composition, on the support substrate after coating. The heat treatment may be performed by using a hot plate or a drying oven, blowing by hot air or hot air, or the like.

The temperature and time when the coating film is heat-treated, the wavelength of light used for light irradiation, the amount of light to be irradiated by the light source, and the like, depending on the type and composition ratio of the compound used in the liquid crystal composition, and the presence or absence of addition of the photopolymerization initiator. The amount of addition or the like is preferably different. Therefore, the conditions regarding the temperature and time of the heat treatment of the coating film, the wavelength of the light used for the light irradiation, and the amount of the light irradiated by the light source described below show only a rough range.

The heat treatment of the coating film is preferably carried out under the condition that uniformity of the polymerizable liquid crystal is obtained. It can also be carried out above the liquid crystal phase transition point of the liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated until the liquid crystal composition exhibits a temperature of the nematic liquid crystal phase, and the liquid crystal composition in the coating film is aligned in the nematic direction. It is also possible to form a nematic alignment by changing the temperature of the coating film in a temperature range in which the liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which the coating film is substantially aligned in the coating film by heating the coating film to a high temperature range in the temperature range, and then the temperature is further lowered to form an orderly alignment. In the case of employing any of the above heat treatment methods, the heat treatment temperature is from room temperature to 120 °C. The temperature is preferably in the range of room temperature to 80 ° C, and more preferably in the range of room temperature to 60 ° C. The heat treatment time is 5 seconds to 2 hours. A preferred range for this time is from 10 seconds to 40 minutes, and a more preferred range is from 20 seconds to 20 minutes. In order to raise the temperature of the layer containing the liquid crystal composition to a predetermined temperature, it is preferred to set the heat treatment time to 5 seconds or longer. In order not to lower the productivity, it is preferred to set the heat treatment time to be within 2 hours. The polymerizable liquid crystal layer of the present invention is obtained in the above manner.

The nematic alignment state of the liquid crystal compound formed in the polymerizable liquid crystal layer is obtained by polymerizing the liquid crystal compound by light irradiation. The wavelength of light used for light irradiation is not particularly limited. Electron beams, ultraviolet rays, visible rays, infrared rays (heat rays), and the like can be used. Usually only use ultraviolet or visible light. The wavelength range is from 150 nm to 500 nm. A preferred range is from 250 nm to 450 nm, and a more preferred range is from 300 nm to 400 nm. Examples of light sources are: low pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lamps), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (ultra high pressure mercury lamps, xenon lamps, mercury lamps). Preferred examples of the light source are metal halide lamps or xenon lamps, ultrahigh pressure mercury lamps, and high pressure mercury lamps. It is also possible to select a wavelength region in which the light source is irradiated by providing a filter or the like between the light source and the polymerizable liquid crystal layer and passing only a specific wavelength region. The amount of light irradiated by the light source is 2 mJ/cm ² to 5000 mJ/cm ² when it reaches the coating film surface. The light amount is preferably in the range of 10 mJ/cm ² to 3000 mJ/cm ² , and more preferably in the range of 100 mJ/cm ² to 2000 mJ/cm ² . The temperature condition at the time of light irradiation is preferably set in the same manner as the heat treatment temperature. Further, the gas atmosphere in the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere, and an air environment, and from the viewpoint of improving hardenability, a nitrogen atmosphere or an inert gas atmosphere is preferred.

The polymerizable liquid crystal layer of the present invention and a liquid crystal film obtained by polymerizing the polymerizable liquid crystal layer by light or heat are used for a plurality of optical elements, or as an optical compensation element used in a liquid crystal display device. In the case of application, the control of the distribution of the inclination angle in the thickness direction becomes extremely important.

One of methods for controlling the tilt angle is a method of adjusting the kind or composition ratio of the liquid crystal compound used in the liquid crystal composition. The tilt angle can also be controlled by adding other components to the liquid crystal composition. The tilt angle of the liquid crystal film can also be controlled according to the kind of the solvent in the liquid crystal composition, the solute concentration, the type or amount of the surfactant added as one of the other components, and the like. The tilt angle of the liquid crystal film may be controlled depending on the type of the support substrate or the polymer film or the rubbing conditions, the drying conditions of the coating film of the liquid crystal composition, the heat treatment conditions, and the like. Further, the irradiation environment or the temperature at the time of irradiation in the photopolymerization step after the alignment also affects the inclination of the liquid crystal film. That is, it is considered that almost all the conditions in the manufacturing process of the liquid crystal film affect the inclination angle. Therefore, it is possible to set an arbitrary inclination angle by appropriately selecting the conditions of the manufacturing process of the liquid crystal film while optimizing the liquid crystal composition.

The parallel alignment distribution is such that the tilt angle is approximately 0 degrees, particularly 0 degrees to 5 degrees, from the substrate surface to the free surface. This alignment state is obtained by applying the liquid crystal composition of the present invention to the surface of a support substrate subjected to surface treatment such as rubbing to form a coating film.

A chiral compound, that is, an optically active compound, may also be added to the liquid crystal composition of the present invention. A preferred example of the optically active compound is a compound represented by the formula (Op-1) to the formula (Op-25). In the above formula, Ak represents an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, and Me, Et and Ph represent a methyl group, an ethyl group and a phenyl group, respectively. P ² is a polymerizable group, and preferably a group containing a (meth) acryl fluorenyloxy group, a vinyloxy group, an oxiranyl group, or an oxetanyl group. The liquid crystal composition of the present invention can be used as a liquid crystal which is a constituent element of a liquid crystal display element, in addition to the raw material of the polymer described below.

[化36]

[化37] Specific examples are described in paragraph 0159 on page 70 of the Japanese Patent Laid-Open Publication No. 2011-148762, and paragraph 0170 on page 81.

Polymerization is carried out by applying a liquid crystal composition containing an appropriate amount of an optically active compound or a liquid crystal composition containing an appropriate amount of an optically active polymerizable compound onto an orientated substrate, thereby obtaining a spiral structure (twisted) Structure) retardation film. The helical structure is fixed by polymerization of the liquid crystal composition. The characteristics of the obtained liquid crystal film depend on the pitch of the obtained spiral structure. The pitch length can be adjusted by the kind and amount of the optically active compound. The optically active compound to be added may be one type, or a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the pitch. Further, the liquid crystal composition may contain other polymerizable compounds in addition to the optically active compound.

The characteristic of the liquid crystal film as described above, that is, the selective reflection of visible light, is a spiral structure that acts on incident light to reflect circularly or elliptically polarized light. The selective reflection characteristic is represented by λ=n·Pitch (λ is the center wavelength of the selective reflection, n is the average refractive index, and Pitch is the pitch), so the [adjustment] center wavelength (λ) can be appropriately prepared by changing n or Pitch. And the wavelength amplitude (Δλ). In order to improve the color purity, the wavelength range (Δλ) may be reduced, and when the reflection in a wide band is required, the wavelength width (Δλ) may be increased. Furthermore, this selective reflection is also greatly affected by the thickness of the polymer. In order to maintain color purity, the thickness must not be made too small. In order to maintain uniform alignment, it is necessary to make the thickness not become too large. Therefore, it is necessary to adjust a moderate thickness, preferably from 0.5 μm to 25 μm, more preferably from 1 μm to 10 μm.

By making the pitch further shorter than visible light, WH de Jeu, "Physical Properties of Liquid Crystalline Materials" (Gordon and Breach, New York (1980)) can be prepared. Negative C plate. In order to shorten the pitch, it is possible to increase the amount of addition by using an optically active compound having a large torque (HTP: helical twisting power). Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. The negative C plate is a Vertical Alignment Nematic (VAN) type, a Vertical Aligned Cholesteric (VAC) type, and an optically compensated birefringence (OCB) suitable for a liquid crystal display element. An optical compensation film for a display element such as a type.

The liquid crystal film can be used as a reflection film having a reflection wavelength region set to near-infrared (wavelength of 800 nm to 2500 nm) as described in Japanese Laid-Open Patent Publication No. 2004-333671, as described in Japanese Laid-Open Patent Publication No. 2004-333671. In order to extend the pitch, it can be achieved, for example, by using an optically active compound having a small torque or by reducing the amount of addition of the optically active compound.

As the optically active compound, any optically active compound can be used as long as it can cause a spiral structure and is appropriately mixed with a liquid crystal composition which is a raw material. Further, it may be either a polymerizable compound or a non-polymerizable compound, and an optimum compound may be added depending on the purpose. In the case of considering heat resistance and solvent resistance, a polymerizable compound is preferred.

Further, among the optically active compounds, a large torque (HTP: helical twisting power) is preferable in terms of shortening the pitch. A representative example of a compound having a large torque is disclosed in GB2298202 and DE10221751.

The thickness (film thickness) of the liquid crystal film has a different appropriate thickness depending on the retardation corresponding to the intended element or the birefringence (value of optical anisotropy) of the liquid crystal film. Therefore, the range of thickness varies for each purpose, but the standard is from 0.05 μm to 100 μm. A more preferred range is from 0.1 μm to 50 μm, and a particularly preferred range is from 0.5 μm to 20 μm. The liquid crystal film preferably has a haze value of 1.5% or less, and preferably has a transmittance of 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. Regarding the transmittance, it is preferred to satisfy these conditions in the visible light region.

The higher the birefringence (value of optical anisotropy) of the liquid crystal film, the thinner the thickness. The thinner the thickness, the better the optical characteristics such as the fog value or the transmittance tend to be. The liquid crystal film is effective as an optical compensation element suitable for a liquid crystal display element (particularly an active matrix type and a passive matrix type liquid crystal display element). Examples of types of liquid crystal display elements suitable for using the liquid crystal film as an optical compensation film are: IPS type (In-Plane Switching), OCB type (Optical Compensated Birefringence) , TN type (Twisted Nematic), STN type (Super Twisted Nematic), ECB type (Electrically Controlled Birefringence), DAP type (integral phase Distortion Arrangement Perpendicular), CSH (Color Super Homeotropic), VAN/VAC (Vertically Aligned Nematic/Cholesteric Phase), OMI (Optical Mode Interference) ), SBE type (Supertwisted Birefringence Effect) and the like. Further, the liquid crystal film may be used as a phase retarder for a display element such as a guest type, a ferroelectric type or an antiferroelectric type. Further, the optimum value of the parameter such as the thickness direction distribution or the thickness of the inclination angle required for the liquid crystal film strongly depends on the type of the liquid crystal display element to be compensated and the optical parameter thereof, and therefore varies depending on the type of the element.

The liquid crystal film may be used as an optical element integrated with a polarizing plate or the like, and in this case, it is disposed outside the liquid crystal cell. On the other hand, the liquid crystal film as the optical compensation element may be disposed inside the liquid crystal cell because the impurity eluted into the liquid crystal filled in the cell does not exist or is small. For example, if the method disclosed in Japanese Laid-Open Patent Publication No. 2008-01943 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on a color filter. Further, the type of the polarizing plate used in the optical element to which the liquid crystal film can be applied is not particularly limited, and is suitable for use in a reflective polarization such as a wire grid polarizing plate, in addition to a widely used iodine-doped absorbing polarizing plate. Optical compensation of the film.

The liquid crystal film may contain an additive such as a dichroic dye. The dichroic dye is preferably a pigment containing hydrazine, naphthoquinone or azobenzene. A parallel alignment liquid crystal film composited with a dichroic dye can also be used as the absorption type polarizing plate. Further, a parallel alignment liquid crystal film which is combined with a fluorescent dye can also be used as a polarization light emitting film. [Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to these examples. <Construction of Structure of Compound> The structure of the synthesized compound was confirmed by measurement of 500 MHz proton NMR (Bruker: DRX-500). The numerical values indicated represent ppm, s represents a single peak, d represents a doublet, t represents a triplet, and m represents a multimodal.

<Phase Transition Temperature> A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope, and the temperature was raised at a rate of 3 ° C/min. The temperature at which the phase is converted to another phase is measured. C means crystal, N means a column phase, S means a dish phase, and I means an isotropic liquid. The NI point is the transition temperature from the upper limit temperature or the nematic phase of the nematic phase to the isotropic liquid. "C 50 N 63 I" was converted from a crystal to a nematic phase at 50 ° C and from a nematic phase to an isotropic liquid at 63 ° C. A single liquid crystal phase is indicated in parentheses.

<Polymerization conditions> Under a nitrogen atmosphere, a 250 W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., Multi-Light-250) was used at room temperature to irradiate 30 mW/cm ² (365 nm). ) The intensity of the light for 30 seconds.

<Evaluation of alignment> (1) Preparation of a glass substrate with a rubbed-treated alignment film On a glass substrate having a thickness of 1.1 mm, spin-coating a low pretilt angle (horizontal alignment mode) with polylysine (Licence calibration) (LIXON Aligner: PIA-5370, manufactured by JNC), after removing the solvent on the spin coating film on a hot plate at 80 ° C, the film was baked in an oven at 230 ° C for 30 minutes. The rayon cloth is used to rub the smoldering person.

(2) Visual observation method The substrate on which the retardation film was formed was sandwiched between two polarizing plates arranged in crossed Nicols, and the substrate was rotated in a horizontal plane to confirm the state of light and dark. The substrate on which the retardation film was formed was subjected to polarization microscope observation to confirm the presence or absence of the alignment defect.

(3) Measurement by Polarization Analyzer A substrate having a retardation film was irradiated with light having a wavelength of 550 nm and 450 nm using an OPTIPRO polarization analyzer manufactured by Shintec. The retardation was measured while reducing the incident angle of these lights from 90° with respect to the film surface. The retardation (also called phase retardation, delay) is represented by Δn × d. The symbol Δn is an optical anisotropy value, and the symbol d is the thickness of the polymer film.

<Measurement of film thickness> A layer of a liquid crystal film of a glass substrate with a liquid crystal film was cut out, and it was measured using a micro shape measuring device (manufactured by KLA TENCOR Co., Ltd., Alpha Step IQ). Step difference.

<Evaluation of Optical Anisotropy (Δn)> The optical anisotropy (Δn) is obtained as a retardation and a film thickness value when the incident angle of light obtained by the liquid crystal film having the parallel alignment is 90° with respect to the film surface. = Calculated by retardation (Re) / film thickness (d).

<Evaluation of Wavelength Dispersion Characteristics> As a characteristic of wavelength dispersion, a value obtained by the following formula was used as an index. Characteristics of wavelength dispersion = retardation measured by light at 450 nm (Re _{450 nm} ) / retardation measured by light at 550 nm (Re _{550 nm} ). In other words, the low wavelength dispersion property of the wavelength-dispersed characteristic value is high, and the reverse wavelength dispersion property is represented by a value of 1 or less.

<Pencil Hardness> Measured according to the method of JIS Standard "JIS-K-5400 8.4 Pencil Scratch Test". In other words, using a pencil hardness meter (C-221 manufactured by Jiguang Seiki Co., Ltd.), the pencil at the time of the occurrence of the flaw was measured on a scratch obtained by using a core of a pencil (Mitsubishi Pencil Uni) fixed at an angle of 45°. The hardness of the core.

[Example 1] The compound (1-1-2-1) shown below was synthesized in the following manner.

[化38] The compound (ex-1) was synthesized in accordance with Heterocyclic Communications 8, 2, 135 (2002).

16.0 g of the compound (ex-1) was added to 160 mL of ethanol, and stirred under a nitrogen atmosphere at 10 ° C or lower. To this was added 5.3 g of sodium borohydride. Then, it was stirred at 10 ° C or lower for 3 hours. 160 mL of 1N hydrochloric acid water was added to the reaction solution, followed by the addition of 160 mL of water. The precipitate was separated by filtration and washed with a large amount of water to obtain 15.5 g of a compound (ex-2).

5.0 g of compound (ex-2), 9.3 g of 4-pentylcyclohexanecarboxylic acid, and 1.1 g of 4-dimethylaminopyridine (DMAP) were added to 90 ml of dichloro In methane, it was stirred while cooling under a nitrogen atmosphere. Thereto, 20 mL of a solution of 9.7 g of 1,3-dicyclohexylcarbodiimide (DCC) in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (yttrium dioxide gel, eluent: toluene) and recrystallized in methanol to obtain 8.2 g of compound (1) -1-2-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-2-1) are as follows. Phase transition temperature (°C): C 95 I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.96 (s, 1H), 7.28 (d, 1H), 7.17 (d, 1H), 3.92 (s, 3H), 2.65 -2.55 (m, 2H), 2.22 (d, 4H), 1.92 (d, 4H), 1.68-1.57 (m, 4H), 1.38-1.19 (m, 18H), 1.07-0.97 (m, 4H), 0.90 (t, 6H).

[Example 2] The compound (1-1-19-1) shown below was synthesized in the following manner.

[39] The compound (ex-3) was synthesized in accordance with Heterocyclic Communications. 8, 2, 135 (2002). 5.0 g of the compound (ex-3), 2.0 g of phenol, and 0.5 g of DMAP were added to 50 mL of dichloromethane, and stirred while cooling under a nitrogen atmosphere. To this was added dropwise a solution of 4.5 g of DCC in dichloromethane (10 mL). After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (yttrium dioxide gel, eluent: toluene) and recrystallized in methanol to obtain 4.8 g of compound (ex -4).

4.8 g of the compound (ex-4) was added to 150 mL of acetonitrile (MeCN), and stirred under a nitrogen atmosphere at room temperature. To this was added dropwise a solution of 17.6 g of an aqueous solution of cerium (IV) ammonium nitrate (CAN) in 45 mL. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Toluene and water were added, and the organic layer was extracted. Further, the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of toluene and methanol, whereby 4.2 g of compound (ex-5) was obtained.

4.2 g of the compound (ex-5) was added to 42 mL of ethanol, and stirred under a nitrogen atmosphere at 10 ° C or lower. To this was added 1.3 g of sodium borohydride. Then, it was stirred at 10 ° C or lower for 3 hours. 40 mL of 1N hydrochloric acid water was added to the reaction solution, followed by the addition of 40 mL of water. The precipitate was separated by filtration and washed with a large amount of water, whereby 4.0 g of a compound (ex-6) was obtained.

4.0 g of the compound (ex-6), 5.8 g of 4-pentylcyclohexanecarboxylic acid, and 0.3 g of DMAP were added to 60 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. A solution of 3.0 g of DCC in dichloromethane (10 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (yttrium dioxide gel, eluent: toluene) and recrystallized in methanol to obtain 4.9 g of compound (1) -1-19-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-19-1) are as follows. Phase transition temperature (°C): C 110 I ¹ H-NMR (CDCl ₃ ; δ ppm): 8.08 (s, 1H), 7.45 (t, 2H), 7.31 (d, 2H), 7.27-7.22 (m, 2H) , 7.19 (d, 1H), 2.65-2.56 (m, 2H), 2.22 (d, 4H), 1.92 (d, 4H), 1.69-1.58 (m, 4H), 1.36-1.19 (m, 18H), 1.07 -0.97 (m, 4H), 0.89 (t, 6H).

[Example 3] The compound (1-1-7-1) shown below was synthesized in the following manner.

[化40] The compound (ex-7) was synthesized in accordance with Heterocyclic Communications. 8, 2, 135 (2002). 5.0 g of the compound (ex-7), 3.2 g of benzyl mercaptan, and 2.9 g of potassium hydroxide were added to 50 ml of N,N-dimethylformamide (DMF) under nitrogen. The mixture was stirred for 4 hours while heating at 100 ° C in an environment. Water was poured into the reaction liquid, and the precipitate was separated by filtration and washed with water and methanol. The obtained crystal was recrystallized in a mixed solution of toluene and methanol, whereby 3.5 g of a compound (ex-8) was obtained.

3.0 g of the compound (ex-8) was added to 90 mL of acetonitrile (MeCN), and stirred under a nitrogen atmosphere at room temperature. To this was added dropwise 18 mL of an aqueous solution of 12.8 g of CAN. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Toluene and water were added, and the organic layer was extracted. Further, the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of toluene and methanol, whereby 1.4 g of the compound (ex-9) was obtained.

1.4 g of the compound (ex-9) was added to 14 mL of ethanol, and stirred under a nitrogen atmosphere at 10 ° C or lower. 0.5 g of sodium borohydride was added thereto. Then, it was stirred at 10 ° C or lower for 3 hours. 14 mL of 1N hydrochloric acid water was added to the reaction solution, followed by the addition of 14 mL of water. The precipitate was separated by filtration and washed with a large amount of water, whereby 1.0 g of a compound (ex-10) was obtained.

20 g of ε-caprolactam, 60 mL of benzyl chloride, and 34 g of potassium hydroxide were added to 300 mL of toluene, and the mixture was stirred under reflux for 6 hours under a nitrogen atmosphere. Water was added, the aqueous layer was extracted, and the aqueous layer was washed with heptane. Concentrated hydrochloric acid was added to make it acidic, toluene was added, and the organic layer was extracted. The organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, whereby 24.4 g of compound (ex-11) was obtained.

25.0 g of trans-4-hydroxycyclohexanecarboxylic acid and 26.3 g of triethylamine were added to 125 mL of DMF, and the mixture was stirred while cooling under a nitrogen atmosphere at 10 ° C or lower. To this, 14.7 g of chloromethyl methyl ether was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added to extract the organic layer, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 2/1)) Purification was carried out and dried under reduced pressure, whereby 25.2 g of compound (ex-12) was obtained.

24 g of the compound (ex-11), 20.3 g of the compound (ex-12), and 2.6 g of DMAP were added to 240 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. A solution of 22.9 g of DCC in dichloromethane (50 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 10/1)) Purification was carried out, whereby 34.3 g of the compound (ex-13) was obtained.

34.3 g of the compound (ex-13) and 2.5 g of Pd/C were added to 400 mL of ethanol, and the mixture was stirred under a hydrogen atmosphere at room temperature for 24 hours using an autoclave. The insoluble matter was separated by filtration, and ethanol was distilled off under reduced pressure, whereby 25.2 g of the compound (ex-14) was obtained.

25.2 g of the compound (ex-14) and 11.0 g of triethylamine were added to 252 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere at 10 ° C or lower. 8.3 g of acrylonitrile chloride was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 8 hours. Water was added, the organic layer was extracted, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 14/1)) Purification was carried out and dried under reduced pressure. The obtained residue and 0.9 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 35 mL of THF and 17.5 mL of 2-propanol (IPA), and heated and stirred at 40 ° C. 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixture of ethyl acetate and heptane, whereby 7.4 g of compound (ex-15) was obtained.

2.8 g of the compound (ex-10), 7.4 g of the compound (ex-15), and 0.6 g of DMAP were added to 75 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. To this was added dropwise 11 mL of a solution of 5.1 g of DCC in dichloromethane. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 10/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 3.6 g of the compound (1-1-7-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-7-1) are as follows. Phase transition temperature ^{(℃): C 62 I 1} H-NMR (CDCl 3; δppm): 7.69 (s, 2H), 7.46 (t, 2H), 7.41 (t, 1H), 7.36 (s, 1H), 7.26 -7.20 (m, 2H), 6.44 (d, 2H), 6.19-6.12 (m, 2H), 5.86 (d, 2H), 4.88-4.80 (m, 2H), 4.20 (t, 4H), 2.76-2.67 (m, 2H), 2.38-2.28 (m, 8H), 2.21-2.13 (m, 4H), 1.90-1.79 (m, 4H), 1.77-1.68 (m, 8H), 1.59-1.42 (m, 8H) .

[Example 4] The compound (1-1-5-1) shown below was synthesized in the following manner.

[化41] 50.0 g of 4-hydroxybutyl acrylate and 50 mL of pyridine were added to 150 mL of toluene, and stirred under a nitrogen atmosphere at room temperature. 72.8 g of toluenesulfonium chloride was slowly added thereto. Then, it was stirred at room temperature for 16 hours. Further, water was added and the mixture was stirred under heating at 40 ° C for 3 hours. The organic layer was extracted, washed with 5% aqueous hydrochloric acid and saturated aqueous sodium hydrogen carbonate, and then washed with water, dried over anhydrous magnesium sulfate, and distilled to remove toluene under reduced pressure. The obtained residue, 59.1 g of hydroquinone, and 148.0 g of potassium carbonate were added to 400 mL of DMF, and the mixture was stirred under heating at 80 ° C for 8 hours under a nitrogen atmosphere. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with saturated aqueous sodium hydrogencarbonate and water, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure, and the residue was subjected to column chromatography (cerium dioxide gel, eluent: The toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 4/1) was purified, whereby 22.9 g of the compound (ex-16) was obtained.

50.0 g of trans-cyclohexanedicarboxylic acid and 38.1 g of potassium carbonate were added to 250 mL of DMF, and the mixture was stirred under heating at 60 ° C under a nitrogen atmosphere. 47.1 g of benzyl bromide was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred at 80 ° C for 6 hours. The organic layer was extracted with toluene and 3N aqueous hydrochloric acid, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, whereby 43.7 g of compound (ex-17) was obtained.

43.7 g of the compound (ex-17) and 33.7 g of triethylamine were added to 400 mL of toluene, and the mixture was stirred while cooling under a nitrogen atmosphere at 10 ° C or lower. 16.1 g of chloromethyl methyl ether was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. Water was added, the organic layer was extracted, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. The toluene was distilled off under reduced pressure, and the residue was purified by column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 10/1)). It was dried under reduced pressure, whereby 32.4 g of a compound (ex-18) was obtained.

32.4 g of the compound (ex-18) and 1.5 g of Pd/C were added to 330 mL of THF, and the mixture was stirred under a hydrogen atmosphere at room temperature for 24 hours using an autoclave. The insoluble material was separated by filtration, and THF was evaporated under reduced pressure. chloroform was added, and the crystals were separated by filtration to obtain 7.1 g of compound (ex-19).

7.7 g of the compound (ex-16), 7.1 g of the compound (ex-19), and 0.8 g of DMAP were added to 80 mL of dichloromethane, and the mixture was stirred while cooling under a nitrogen atmosphere. A solution of 7.0 g of DCC in dichloromethane (15 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 8/1)) Purification was carried out and dried under reduced pressure. The obtained residue and 0.3 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 15 mL of THF and 7.5 mL of 2-propanol (IPA), and the mixture was stirred under heating at 40 ° C for 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixture of ethyl acetate and heptane, whereby 3.3 g of compound (ex-20) was obtained.

1.0 g of the compound (ex-10) described in Example 3, 3.3 g of the compound (ex-20), and 0.2 g of DMAP were added to 40 mL of dichloromethane, and stirred while cooling under a nitrogen atmosphere. . To this was added dropwise a solution of 1.8 g of DCC in dichloromethane (5 mL). After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 4/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 1.8 g of the compound (1-1-5-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-5-1) are as follows. Phase transition temperature (°C): C 129 N 180<I ("180<I" is as follows: although the polymerization point cannot be measured at about 180 °C, it is expected to exist above 180 °C if it is not polymerized. from opposing isotropic liquid transition temperature of the nematic _{^{transition) 1 H-NMR (CDCl 3}} ; δppm): 7.70 (d, 2H), 7.44 (t, 2H), 7.41-7.36 (m, 2H), 7.16-7.11 (m, 2H), 7.00 (d, 4H), 6.90 (d, 4H), 6.41 (d, 2H), 6.17-6.09 (m, 2H), 5.83 (d, 2H), 4.24 (t, 4H), 3.99 (t, 4H), 2.78-2.69 (m, 2H), 2.67-2.59 (m, 2H), 2.43-2.30 (m, 8H), 1.93-1.67 (m, 16H).

[Example 5] The compound (1-1-6-1) shown below was synthesized in the following manner.

[化42] 50.0 g of 6-chlorohexanol, 66.0 g of methyl 3-(4-hydroxyphenylpropionate), 49.2 g of potassium carbonate, and 6.1 g of potassium iodide were added to 330 mL of DMF under nitrogen atmosphere. The mixture was heated and stirred at 80 ° C for 10 hours. Toluene and water were added, and the organic layer was extracted, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, dried over anhydrous magnesium sulfate, and distilled to remove toluene under reduced pressure. The obtained residue and 22.6 g of potassium hydroxide were added to 260 mL of methanol and 260 mL of water, and the mixture was stirred under reflux for 3 hours under a nitrogen atmosphere. Methanol was distilled off under reduced pressure, ethyl acetate and 3N aqueous hydrochloric acid were added, and the organic layer was extracted. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was evaporated under reduced pressure, and the residue was recrystallized from a mixture of toluene and ethanol to obtain 69.2 g of compound (ex-21). .

69.2 g of the compound (ex-21) and 44.1 g of dimethylaniline were added to 700 mL of toluene, and the mixture was stirred while cooling under a nitrogen atmosphere at 10 ° C or lower. 28.2 g of acrylonitrile chloride was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred under heating at 40 ° C for 4 hours. Water was added, the organic layer was extracted, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was recrystallized from toluene, whereby 50.0 g of compound (ex-22) was obtained.

42.9 g of the compound (ex-22), 25.2 g of the compound (ex-12) described in Example 3, and 3.3 g of DMAP were added to 430 mL of dichloromethane, and stirred while cooling under a nitrogen atmosphere. . A solution of 29.0 g of DCC in dichloromethane (60 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate was separated by filtration, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 12/1)) Purification was carried out and dried under reduced pressure. The obtained residue and 2.1 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 110 mL of THF and 55 mL of IPA, and the mixture was stirred under heating at 40 ° C for 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixture of ethyl acetate and heptane to obtain 31.8 g of compound (ex-23).

3.2 g of the compound (ex-10) described in Example 3, 12.1 g of the compound (ex-23), and 0.7 g of DMAP were added to 40 mL of dichloromethane, and stirred while cooling under a nitrogen atmosphere. . A solution of 5.9 g of DCC in dichloromethane (12 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 4/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 10.7 g of the compound (1-1-6-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-1) are as follows. Phase transition temperature (°C): C 90 (N 70) I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.67 (d, 2H), 7.44 (t, 2H), 7.38 (t, 1H), 7.33 (s, 1H), 7.15-7.08 (m, 6H), 6.83 (d, 4H), 6.40 (d, 2H), 6.17-6.08 (m, 2H), 5.81 (d, 2H), 4.85-4.76 (m, 2H) , 4.17 (t, 4H), 3.94 (t, 4H), 2.90 (t, 4H), 2.73-2.65 (m, 2H), 2.62 (t, 4H), 2.31-2.24 (m, 4H), 2.15-2.07 (m, 4H), 1.86-1.67 (m, 12H), 1.56-1.41 (m, 12H).

[Example 6] The compound shown below (1-1-6-) was synthesized by the same method except that the benzyl mercaptan was changed to 4-chlorobenzyl mercaptan in the synthesis method described in Example 3. 2).

[化43]

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-2) are as follows. Phase transition temperature (°C): C 90 (N 39) I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.60 (d, 2H), 7.41 (d, 2H), 7.30 (s, 1H), 7.15-7.08 ( m, 6H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.09 (m, 2H), 5.81 (d, 2H), 4.84-4.76 (m, 2H), 4.17 (t, 4H) , 3.94 (t, 4H), 2.90 (t, 4H), 2.72-2.58 (m, 6H), 2.31-2.23 (m, 4H), 2.15-2.07 (m, 4H), 1.86-1.67 (m, 12H) , 1.56-1.42 (m, 12H).

[Example 7] The compound (1-1-15-1) shown below was synthesized in the following manner.

[化44] 5.0 g of the compound (ex-3) described in Example 2 and 0.02 mL of DMF were added to 30 mL of sulfinium chloride, and the mixture was stirred under reflux for 1 hour under a nitrogen atmosphere. The sulfinium chloride was distilled off under reduced pressure, toluene was further added, and toluene was distilled off under reduced pressure. The obtained residue was added to 100 mL of THF, and stirred under a nitrogen atmosphere at 10 ° C or lower. 2.6 g of 2-aminobenzenethiol was added dropwise thereto. After the dropwise addition, the mixture was stirred at 10 ° C or lower for 1 hour, and further 2.3 g of triethylamine was added. After the addition, the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and water and dried over anhydrous magnesium sulfate. The THF and ethyl acetate were distilled off under reduced pressure, and the residue was subjected to column chromatography (cerium dioxide gel, eluent: toluene-dichloromethane mixture (volume ratio: toluene/dichloromethane = 2/1) () Purification was carried out and dried under reduced pressure, whereby 1.2 g of compound (ex-24) was obtained.

1.2 g of the compound (ex-24) was added to 24 mL of acetonitrile (MeCN), and stirred under a nitrogen atmosphere at room temperature. To this was added dropwise 10 mL of an aqueous solution of 4.2 g of CAN. After the dropwise addition, the mixture was stirred at room temperature for 4 hours. Methylene chloride and water were added, and the organic layer was extracted. Further, the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, whereby 1.0 g of compound (ex-25) was obtained.

1.0 g of the compound (ex-25) was added to 10 mL of ethanol, and stirred under a nitrogen atmosphere at 10 ° C or lower. To this was added 0.3 g of sodium borohydride. Then, it was stirred at 10 ° C or lower for 3 hours. 10 mL of 1N hydrochloric acid water was added to the reaction solution, followed by the addition of 10 mL of water. The precipitate was separated by filtration and washed with a large amount of water, whereby 0.9 g of a compound (ex-26) was obtained.

0.9 g of the compound (ex-26), 2.8 g of the compound (ex-23) described in Example 5, and 0.2 g of DMAP were added to 30 mL of dichloromethane, and stirred while cooling under a nitrogen atmosphere. . A solution of 1.3 g of DCC in dichloromethane (5 mL) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 4/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 1.0 g of the compound (1-1-15-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-15-1) are as follows. Phase transition temperature (°C): C 104 (N 79) I ¹ H-NMR (CDCl ₃ ; δ ppm): 8.10 (d, 1H), 7.91 (d, 1H), 7.71 (s, 1H), 7.53 (t, 1H), 7.44 (t, 1H), 7.24 (d, 1H), 7.18-7.11 (m, 5H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.09 (m, 2H), 5.81 (d, 2H), 4.87-4.77 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 2.92 (t, 4H), 2.77-2.58 (m, 6H), 2.34-2.24 (m , 4H), 2.18-2.09 (m, 4H), 1.87-1.67 (m, 12H), 1.57-1.42 (m, 12H).

[Example 8] The compound (1-1-20-1) shown below was synthesized in the following manner.

[化45] 8.0 g of 4-bromomethylbiphenyl and 9.8 g of potassium carbonate were added to 40 ml of THF, and stirred under a nitrogen atmosphere at room temperature. 3.0 g of thioacetic acid was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 40 ml of MeOH was added to the reaction liquid, followed by stirring for 1 hour. The mixture was neutralized by dropwise addition of a 3N aqueous hydrochloric acid solution, and ethyl acetate was added to extract. Further, the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 6.4 g of compound (ex-27).

5.5 g of compound (ex-7), 5.8 g of compound (ex-27), and 4.0 g of potassium carbonate were added to 55 ml of N,N-dimethylformamide (DMF) in a nitrogen atmosphere. The mixture was stirred under heating at 60 ° C for 4 hours. 1.6 g of potassium hydroxide was added thereto, and stirred at 100 ° C for 1 hour. Water was poured into the reaction liquid, and the precipitate was separated by filtration and washed with water and methanol. The obtained crystal was recrystallized in a mixed solution of toluene and methanol, whereby 2.4 g of a compound (ex-28) was obtained.

2.0 g of the compound (ex-28) was added to 60 mL of acetonitrile (MeCN), and stirred under a nitrogen atmosphere at room temperature. Thereto, 35 mL of an aqueous solution of 6.2 g of cerium (IV) ammonium nitrate (CAN) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Methylene chloride and water were added for extraction, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, whereby 1.3 g of compound (ex-29) was obtained.

1.3 g of the compound (ex-29) was added to 13 mL of ethanol, and stirred under a nitrogen atmosphere at 10 ° C or lower. To this was added 0.3 g of sodium borohydride. Then, it was stirred at 10 ° C or lower for 3 hours. 13 mL of 1N hydrochloric acid water was added to the reaction solution, followed by the addition of 13 mL of water. The precipitate was separated by filtration and washed with a large amount of water, whereby 1.3 g of a compound (ex-30) was obtained.

3.7 g of compound (ex-23), 1.3 g of compound (ex-30), and 0.2 g of N,N-dimethyl-4-aminopyridine (DMAP) were added to 37 mL of dichloromethane. Stir under cooling in a nitrogen atmosphere. Thereto, 4 g of a solution of 1.8 g of N,N'-dicyclohexylcarbodiimide (DCC) in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 10/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 1.6 g of the compound (1-1-20-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-20-1) are as follows. Phase transition temperature (°C): C 103 I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.75 (d, 2H), 7.69-7.62 (m, 4H), 7.48 (t, 2H), 7.41-7.36 (m, 2H), 7.15-7.09 (m, 6H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85-4.77 (m, 2H) , 4.17 (t, 4H), 3.94 (t, 4H), 2.91 (t, 4H), 2.74-2.57 (m, 6H), 2.33-2.25 (m, 4H), 2.16-2.08 (m, 4H), 1.87 -1.66 (m, 12H), 1.55-1.41 (m, 12H).

[Example 9] The compound shown below (1-1) was synthesized by the same method except that 4-bromomethylbiphenyl was changed to 4-cyanobenzyl bromide in the synthesis method described in Example 8. -6-3).

[Chem. 46]

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-3) are as follows. Phase transition temperature (°C): C 109 I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.78 (d, 2H), 7.73 (m, 2H), 7.44 (s, 1H), 7.19-7.08 (m, 6H) , 6.93 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85-4.77 (m, 2H), 4.17 (t, 4H), 3.94 (t , 4H), 2.91 (t, 4H), 2.74-2.57 (m, 6H), 2.33-2.23 (m, 4H), 2.16-2.07 (m, 4H), 1.87-1.66 (m, 12H), 1.55-1.41 (m, 12H).

[Example 10] The compound shown below was synthesized by the same method except that the 4-bromomethylbiphenyl was changed to 4-trifluoromethylbenzyl bromide in the synthesis method described in Example 8. -1-6-4).

[化47]

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-4) are as follows. Phase transition temperature (°C): C 119(N 35)I ¹ H-NMR (CDCl ₃ ; δ ppm): 7.78 (d, 2H), 7.70 (m, 2H), 7.41 (s, 1H), 7.18-7.10 ( m, 6H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85-4.77 (m, 2H), 4.17 (t, 4H) , 3.94 (t, 4H), 2.91 (t, 4H), 2.74-2.57 (m, 6H), 2.33-2.23 (m, 4H), 2.16-2.07 (m, 4H), 1.87-1.66 (m, 12H) , 1.55-1.41 (m, 12H).

[Example 11] The compound (1-1-21-1) shown below was synthesized in the following manner.

[48] 5.0 g of compound (ex-3), 2.9 g of benzamidine, and 0.5 g of N,N-dimethyl-4-aminopyridine (DMAP) were added to 100 mL of dichloromethane. Stir under cooling in a nitrogen atmosphere. Thereto, 8 mL of a solution of 4.4 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) in dichloromethane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. Water was added to the reaction liquid, the crystals were separated by filtration, and the obtained crystals were washed with water and dichloromethane to obtain 5.4 g of compound (ex-31).

5.3 g of the compound (ex-31) and 5.8 g of diisopropyl ethylamine (DIPEA) were added to 265 ml of acetonitrile, and stirred under a nitrogen atmosphere at room temperature. 11.3 g of tosylhydrazine chloride (TsCl) potassium hydroxide was added thereto, followed by stirring at room temperature for 16 hours. The crystals were separated by filtration, and the obtained crystals were washed with water and methanol, whereby 4.8 g of compound (ex-32) was obtained.

3.8 g of the compound (ex-32) was added to 76 mL of dichloromethane, and stirred under a nitrogen atmosphere at -70 ° C or lower. To this was added dropwise 6.2 g of boron tribromide. After the dropwise addition, the mixture was stirred at -70 ° C or lower for 2 hours, followed by stirring at room temperature for 8 hours. The reaction liquid was added to water, and the precipitated crystals were washed with water and methanol to obtain 3.2 g of a compound (ex-33).

5.0 g of compound (ex-23), 1.7 g of compound (ex-33), and 0.3 g of N,N-dimethyl-4-aminopyridine (DMAP) were added to 50 mL of dichloromethane. Stir under cooling in a nitrogen atmosphere. Thereto was dropwise added 5 g of a solution of 2.4 g of N,N'-dicyclohexylcarbodiimide (DCC) in dichloromethane. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitate which precipitated was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (yttrium dioxide gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene/ethyl acetate = 10/1)) Purification was carried out, and recrystallization was carried out in methanol, whereby 3.2 g of the compound (1-1-21-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-21-1) are as follows. Phase transition temperature (°C): C 122 (N 99) I ¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 2H), 7.90 (s, 1H), 7.63-7.55 (m, 3H), 7.30 ( d, 1H), 7.21 (d, 1H), 7.13 (d, 4H), 6.84 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85 -4.77 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 2.91 (t, 4H), 2.74-2.57 (m, 6H), 2.33-2.25 (m, 4H), 2.16-2.08 (m, 4H), 1.87-1.66 (m, 12H), 1.55-1.41 (m, 12H).

<Preparation of Liquid Crystal Composition> [Example 12] The compound of the present invention synthesized as described above and the compound (M2-7-1), the compound (M1-15-1), and the compound (M1-16-1) shown below were used. And the compound (M1-17-1) to prepare a liquid crystal composition (S-1 to S-12).

[48] The type and content of the compound of the present invention in the liquid crystal composition, the type and content of other polymerizable liquid crystal compound, the content of the polymerization initiator, the content of the surfactant, and the content of the solvent are shown in Table 1. Here, in Table 1, % represents the weight % of each material when the total weight of a liquid crystal composition is 100 weight%. The polymerization initiator was IrGacure 907 (manufactured by BASF Co., Ltd.), and the surfactant was used by Ftergent FTX-218 (manufactured by Neos Co., Ltd.). A mixed solution of cyclopentanone and toluene (mixing ratio of cyclopentanone-toluene was 1/1 by weight).

[Table 1]

[Example 13] <Preparation of liquid crystal composition> A liquid crystal composition was produced in the same manner as in Example 12. Among them, the polymerization initiator was made using ADEKA ARKLS NCI-930 (made by ADEKA), and the solvent used cyclohexanone. [Table 2]

[Comparative Example 1] The compound (M2-7-1), the compound (M1-15-1), and the compound (M1-16-1) were used in the same manner as in the method described in Example 12, and the following The liquid crystal composition (SC-1 to SC-3) was produced by the compound (C-1).

[化49]

[table 3]

<Preparation of Optically Anisotropic Film> [Example 14] The liquid crystal composition (S-1) to liquid crystal composition (S-12) produced in Example 12 and Example 13 was applied to a belt by spin coating. On the glass substrate with the rubbed alignment film. The substrate was heated at 80 ° C for 2 minutes, and cooled at room temperature for 1 minute, and the polymerizable liquid crystal layer from which the solvent was removed was polymerized in the air by ultraviolet rays to obtain an optically anisotropic film in which the alignment state of the liquid crystal was fixed. . These optical anisotropic films were confirmed by a polarizing microscope observation and a polarization analyzer, and as a result, there was no alignment defect and uniform parallel alignment.

[Comparative Example 2] An optically anisotropic film was obtained from the liquid crystal composition (SC-1) to the liquid crystal composition (SC-3) produced in Comparative Example 1 in the same manner as in the method described in Example 14. When the optically anisotropic film obtained was confirmed by a polarizing microscope observation and a polarization analyzer, it was confirmed that (SC-1) and (SC-2) had no alignment defects and had a uniform parallel alignment; SC-3) precipitates crystals to produce alignment defects, and a film having uniform parallel alignment is not obtained.

When (SC-3) and (S-6) are compared, it is understood that when the liquid crystal compound (1) of the present invention is used, it is possible to form a uniform parallel which is difficult to form when only the compound (C-1) is used. Aligned membrane.

<Optical Characteristics of Optically Anisotropic Film> [Examples 15 to 26, Comparative Examples 3 to 4] The film surface of the optically anisotropic film produced in Example 14 and Comparative Example 2 was The measured value (Re ₄₅₀ ) at a wavelength of 450 ° and the measured value (Re ₅₅₀ ) at a wavelength of 550 nm, the film thickness, Δn at a wavelength of 550 nm, and the wavelength dispersion characteristics are shown in Tables 4 and 5.

[Table 4]

[table 5]

The optically anisotropic films of Examples 15 to 26 showed a low value in wavelength dispersion characteristics as compared with Comparative Example 3. This supports the case where the effect of lowering the wavelength dispersion property is exhibited by incorporating the compound of the present invention into the liquid crystal composition, and it is understood that the wavelength dispersion property of the obtained optically anisotropic film can be controlled by using the compound of the present invention. . Further, in the optically anisotropic film of Example 20, the wavelength dispersion property showed a value of 1 or less, and it was confirmed that the wavelength dispersion characteristic was reversed.

<Heat resistance of optical properties of optically anisotropic film> The following results are shown in Tables 6 and 7, and the results are shown in 200 with respect to the optical anisotropic film produced in Example 14 and Comparative Example 2. The film surface after simmering for 30 minutes at ° C was measured at a retardation of a wavelength of 550 nm of 90 degrees. Here, in Tables 6 and 7, the residual Re represents the value of Re after calcination at 200 ° C for 30 minutes when the initial Re value is set to 100.

[Table 6]

[Table 7]

In the optically anisotropic films of Examples 17 to 26, compared with Comparative Example 3 and Comparative Example 4, the residual ratio of retardation after calcination at 200 ° C for 30 minutes was large. That is, it can be seen that the change in optical characteristics due to heat is small.

<Mechanical Properties of Optically Anisotropic Film> The results of measuring the mechanical strength of the film surface of the optically anisotropic film produced in Example 14 and Comparative Example 2 by the pencil hardness test are shown in Tables 8 and 9. Here, in Tables 8 and 9, the hardness (parallel) indicates the hardness of the core of the pencil when the scratch is formed in the direction parallel to the direction in which the optical anisotropic film is aligned, and the hardness (vertical) The hardness of the core of the pencil when the scratch is formed in the direction perpendicular to the direction in which the optical anisotropic film is aligned.

[Table 8]

[Table 9]

<Preparation of Liquid Crystal Composition> [Example 27] A liquid crystal composition (S-13) was produced by using the compound of the present invention and the compound (M2-1-1) and the compound (M1-12-1) shown below.

[化50] These compounds were mixed in a weight ratio of the compound (1-1-6-1): compound (M2-1-1): compound (M1-12-1) = 33:33:34. This composition was designated as MIX1. For the MIX1, GA-1000 (manufactured by Osaka Gas Chemical Co., Ltd.) having a weight ratio of 0.10 and Irgacure 907 (manufactured by BASF Co., Ltd.) having a weight ratio of 0.06 were added. Further, cyclohexanone was added to prepare a liquid crystal composition (S-13) having a solvent ratio of 75% by weight.

<Preparation of Optically Anisotropic Film> [Example 28] The liquid crystal composition (S-13) produced in Example 27 was applied to a glass substrate by spin coating (slide glass: S- 1112). The substrate was heated at 80 ° C for 2 minutes, and cooled at room temperature for 1 minute. The coating film from which the solvent was removed was polymerized under a nitrogen stream by ultraviolet rays to obtain a liquid crystal film having a uniform vertical alignment.

<Optical Characteristics of Optically Anisotropic Film> [Example 29] Measurement of a wavelength of 450 nm in a slow axis direction with respect to the film surface of the optically anisotropic film produced in Example 28 The wavelength dispersion characteristic calculated from the value (Re ₄₅₀ ) and the measured value (Re ₅₅₀ ) at a wavelength of 550 nm was 1.0439. [Industrial Applicability] The compound of the present invention has low-wavelength dispersion characteristics or reverse-wavelength dispersion characteristics, and exhibits a liquid crystal phase at a relatively low temperature, and a liquid crystal composition using the compound is easy to control wavelength dispersion characteristics, and Since it is excellent in compatibility and solubility, an optical anisotropic film can be easily obtained. In addition, the obtained optically anisotropic film has high mechanical strength or heat resistance. Therefore, the film containing the polymer is suitable, for example, for a retardation film, an optical compensation film, a reflective film, a selective reflection film, an antireflection film, a viewing angle compensation film, a liquid crystal alignment film, a polarizing element, a circularly polarizing element, and an elliptically polarized film. Components and the like, as well as display elements having these films or elements.

no

no

Claims (20)

A liquid crystalline compound which is a compound represented by the formula (1): In the formula (1), A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a pyridine-2,5-diyl group, Or naphthalene-2,6-diyl, of which at least one hydrogen may be via fluorine, chlorine, cyano, hydroxy, formamyl, trifluoroethenyl, difluoromethyl, trifluoromethyl, carbon The alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the alkyl ester having 1 to 5 carbon atoms or the alkyl fluorenyl group having 1 to 5 carbon atoms are substituted; and Z ¹ and Z ² are each independently a single Bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF _{2 -, - CH 2 CH 2 -} , - CF 2 CF 2 -, - OCH 2 CH 2 O -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 - , -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N =N- or -C≡C-; m and n are each independently an integer from 0 to 3 and are in the relationship of 1≦m+n≦4; X ¹ is -O-, -S- or -NR ³ - R ³ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkyl fluorenyl group having 1 to 5 carbon atoms; Q ¹ is hydrogen, a halogen or a monovalent organic group; and R ¹ and R ² are each independently hydrogen and fluorine. Chlorine, three a methyl group, a trifluoromethoxy group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl ester having 1 to 20 carbon atoms, or a group represented by the formula (2); In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or an alkylene group having a carbon number of 1 to 20, the alkylene At least one of -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-; PG is of formula (PG-1) to formula (PG-8) a polymerizable group represented by any of; In the formulae (PG-1) to (PG-8), R ^{4 is} each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl. The liquid crystalline compound according to claim 1, wherein in the formula (1), Q ¹ is a group represented by the formula (3) or the formula (4). In the formulae (3) and (4), Z ^{3 is} independently a single bond, -COO- or -COS-; Z ^{4 is} independently a single bond, -CH=CH-, -N=CH-, - CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-; R ⁵ is hydrogen, fluorine, chlorine, cyano, alkane having 1 to 20 carbon atoms Further, -CH ₂ - in the alkyl group may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, wherein the hydrogen in the alkyl group may be replaced by a halogen A ^{3 is} independently a bivalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, and A ⁴ is a monovalent 5-membered ring or a 6-membered aromatic ring, or a fused ring thereof. At least one hydrogen of the aromatic ring of A ³ and A ⁴ or a fused ring thereof may be fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms, an alkylhydrazine group having 1 to 5 carbon atoms or a thioalkyl group having 1 to 5 carbon atoms; p is an integer of 0 to 2 . The liquid crystalline compound according to claim 1, wherein in the formula (1), at least one of R ¹ and R ² is a group represented by the formula (2). The liquid crystalline compound according to claim 1, wherein in the formula (1), X ¹ is -S-. The liquid crystalline compound according to claim 1, wherein in the formula (1), A ¹ and A ² are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group. Among these groups, At least one hydrogen may be fluorine, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkane having 1 to 5 carbon atoms. Substituted; Z ¹ and Z ² are independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -. The liquid crystalline compound according to claim 1, wherein in the formula (1), Q ¹ is a group represented by the formula (4). In the formula (4), Z ³ is a single bond, -COO- or -COS-; Z ⁴ is a single bond, and A ^{3 is} independently a divalent 5-membered ring or a 6-membered ring aromatic ring, or a thick one thereof Ring, A ⁴ is a monovalent 5-membered or 6-membered aromatic ring, or a fused ring thereof, and at least one hydrogen of the aromatic ring of A ³ and A ⁴ or their fused ring may be fluorine, chlorine or cyanide a group, a nitro group, a trifluoromethyl group, a trifluoromethoxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms, and a carbon number of 1 to 5 The alkyl alkane group or a thioalkyl group having 1 to 5 carbon atoms is substituted, and p is an integer of 0 or 1. The liquid crystalline compound according to claim 1, wherein in the formula (1), at least one of A ¹ and A ² is a 1,4-cyclohexylene group. The liquid crystalline compound according to claim 1, wherein in the formula (1), at least one of Z ¹ and Z ² is -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -. The liquid crystalline compound according to claim 1, wherein, in the formula (1), R ¹ and R ² are a group represented by the formula (2-1). In the formula (2-1), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-, Y ² is a single bond or an alkylene group having a carbon number of 1 to 20, At least one -CH ₂ - in the alkylene group may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-, and R ⁴ is hydrogen or methyl. The liquid crystalline compound according to the first aspect of the invention, wherein in the formula (1), Q ¹ is a group represented by any one of the formulae (4-1) to (4-9). In the formulae (4-1) to (4-9), X ² is -O- or -S-, at least one -CH= may be substituted by -N=, and at least one hydrogen may be fluorine, chlorine or cyano a trifluoroethenyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms. Replaced; * indicates the bonding site. A liquid crystal composition containing at least one of the liquid crystalline compounds according to claim 1 of the patent application. A liquid crystal composition containing at least one of the liquid crystalline compounds according to claim 1 and at least one selected from the group consisting of compounds represented by formula (M1) and formula (M2). In the formula (M1) and the formula (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, pyridine-2,5-di. a base, an anthrone-2,7-diyl or a naphthalene-2,6-diyl group, wherein at least one of the hydrogens may be a fluorine, a chlorine, a cyano group, a hydroxyl group, a methyl group, a trifluoroethyl group, Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms or alkyl anthracene having 1 to 5 carbon atoms ; Z ^M are independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, - CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ - , -CH=CH-, -N=CH-, -CH=N-, -N=CCH ₃ -, -CCH ₃ =N-, -N=N- or -C≡C-; X ^M is hydrogen, Fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or carbon number 1 to An alkyl ester of 20; q is an integer from 1 to 4; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO -. A liquid crystal composition containing at least one of a liquid crystalline compound according to claim 1 and at least one compound represented by formula (M1), In the formula (M1), A ^{M is} independently 1,4-phenylene or 1,4-cyclohexylene, and at least one of A ^M is 1,4-cyclohexylene, and at least one of these groups may be a fluorine, a chlorine, a trifluoroethenyl group, a difluoromethyl group, a trifluoromethyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms or Substituted with alkanoyl group having 1 to 5 carbon atoms; Z ^{M is} independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ -; q is an integer of 1 or 2; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkane having 1 to 20 carbon atoms a base, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl ester having 1 to 20 carbon atoms; a is an integer of 0 to 20; R ^M is hydrogen or a methyl group, and Y ^M is Single bond, -O-, -COO-, -OCO- or -OCOO-. The liquid crystal composition according to claim 1, which further contains at least one chiral compound. The liquid crystal composition according to claim 1, which further comprises at least one dichroic dye compound. A polymer obtained by irradiating ultraviolet light to a liquid crystal composition as described in claim 11 of the patent application. An optically anisotropic film which is optically anisotropic as described in claim 16 of the patent application. A polarizing plate comprising the optically anisotropic film according to item 17 of the patent application. A display element comprising the optically anisotropic film according to claim 17 of the patent application. A display element comprising the polarizing plate of claim 18 of the patent application.