TWI659090B - Liquid crystal compound, liquid crystal composition, polymer and application thereof - Google Patents

Abstract

The present invention provides a liquid crystal compound, a liquid crystal composition, a polymer, an optically anisotropic film, and a polarizing plate that can control the refractive index anisotropy due to wavelength and exhibit low-wavelength dispersion characteristics and further exhibit inverse wavelength dispersion. Display elements. The present invention is a compound represented by the following formula (1) and a liquid crystal composition containing the compound.

Description

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

The present invention relates to a liquid crystal compound having a benzothiophene, benzofuran or indole structure, a liquid crystal composition containing the compound, a polymer obtained from the liquid crystal composition, an optically anisotropic film, and What they do.

In recent years, liquid crystal compounds having a polymerizable group have been flexibly applied to optically anisotropic films that exhibit birefringence (optical anisotropy), such as reflective polarizers and retardation plates. This compound exhibits birefringence in a liquid crystal state, and its orientation is fixed by polymerization. The fixed alignment state of the polymer includes homogeneous (horizontal alignment), tilt (tilt alignment), vertical (homeotropic) (vertical alignment), and twist (twisted alignment).

An optically anisotropic film having parallel alignment can be used as a composite retardation plate or a circular polarizer by combining it with a 1/2 wavelength plate, a 1/4 wavelength plate, or a film having other optical functions, for example (see Patent Documents) 1).

The optical axis of the optically anisotropic film with vertical alignment is in the n _z direction, and the refractive index in the optical axis direction is greater than the refractive index in the orthogonal direction, so it is classified as a positive C-plate in the refractive index ellipsoid. . The positive C-plate can be combined with a film having other optical functions, and is used for optical compensation in a liquid crystal mode of horizontal alignment such as an in-plane switching (IPS) mode, such as the field of view of a polarizer Improvement of angular characteristics (Non-Patent Document 1 to Non-Patent Document 3, Patent Document 2 and Patent Document 3).

The optical characteristics required for the optically anisotropic film vary depending on the use or purpose, and a variety of liquid crystal compounds have been developed as the compounds to be used. In addition, since it is often difficult to control the anisotropy alone, it is used as a liquid crystal composition in combination with a plurality of compounds.

Such a liquid crystal composition is used as an ink by dissolving it in an organic solvent for the purpose of adjusting coating properties and the like. When a liquid crystal composition is used to produce a film having optical anisotropy, a liquid crystal compound, a photopolymerization initiator, a surfactant, and the like are dissolved in an organic solvent to prepare an adjusted ink such as solution viscosity and leveling property. This ink was applied to an alignment-treated substrate, and the solvent was dried to align the liquid crystal composition on the substrate. Subsequently, it is irradiated with ultraviolet rays to polymerize and fix the alignment state. Generally, the organic solvent is dried and removed until polymerization is performed at room temperature. During this period, it is necessary to maintain a uniform liquid crystal state without causing precipitation of crystals and 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 organic solvents, and further have long-term liquid crystallinity around room temperature. In addition, regarding organic solvents, in consideration of environmental load or impact on the human body, it is required to have high solubility in organic solvents having high safety.

Furthermore, in addition to the optically anisotropic properties of the polymer obtained from the liquid crystal composition, high transparency, high mechanical strength, high adhesion to the substrate, low shrinkage, high heat resistance, and high Chemical resistance and other characteristics.

In an optically anisotropic layer formed of rod-shaped molecules, generally, the two refractive indices of an anisotropic molecule, ne (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 with increasing wavelength. At this time, compared with no, the refractive index change rate of ne to the wavelength is large, so the refractive index anisotropy (Δn = ne-no) decreases as the application wavelength becomes larger. On the other hand, in a display device such as a liquid crystal display (LCD), the light source is white light including light having a wavelength of about 380 nm to 800 nm, but it is designed using a general optical anisotropic layer 1 / When a 2λ or 1 / 4λ plate is used in combination, the following problems arise due to the wavelength dispersion described above: a change in the polarization state due to the wavelength occurs, and the light becomes colored. In order to prevent this problem, it is necessary to control the wavelength dispersion in order to be a phase difference designed at each wavelength, and a material having low dependence on refractive index anisotropy due to wavelength (low-wavelength dispersion characteristic) or a wavelength dependent A material whose refractive index anisotropy becomes larger (inverse wavelength dispersion characteristics).

In order to obtain an optically anisotropic layer having inverse wavelength dispersion characteristics, a method of laminating two retardation layers at different angles in the direction of refractive index anisotropy has been proposed (Patent Document 4 and Patent Document 5). However, such a laminated body has the following problems: two retardation layers are required, and the anisotropy angle of the two retardation layers needs to be adjusted, etc., manufacturing complexity for forming the laminated body, and optical anisotropy. The film thickness of the layer becomes thicker and the like.

In recent years, in order to solve the problem, an optically anisotropic layer having reverse wavelength dispersion without lamination is required, and liquid crystal compounds having reverse wavelength dispersion characteristics have been proposed (Patent Documents 6 to 10).

However, since the compound described in Patent Document 6 has a low refractive index anisotropy, it is necessary to thicken the film in order to obtain a desired retardation. In addition, there is a concern that it is difficult to control alignment uniformity due to a small aspect ratio, and further, It is difficult to manufacture due to the long synthesis path. Since the compounds described in Patent Documents 7 and 8 have absorption in the visible region, they are liable to cause a decrease in transmittance, staining, and the like, and are not suitable for use in optical applications. The compounds described in Patent Literature 9 and Patent Literature 10 are relatively good in terms of optical characteristics and manufacturing processes, but further improvements in mechanical strength of the polymer, adhesion to the substrate, and heat resistance are required. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2002-372623 [Patent Literature 2] International Publication No. 05 / 38517A1 [Patent Literature 3] US Patent Application Publication No. 2006/182900 [Patent Literature 4] Japanese Patent Laid-Open Publication 10-068816 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2001-004837 [Patent Literature 6] Japanese Patent Publication No. 2010-522893 [Patent Literature 7] Japanese Patent Publication No. 2009-179563 [Patent Literature 8] International Publication No. 2012 / 169424A1 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2005-289980 [Patent Literature 10] Japanese Patent Laid-Open Publication No. 2010-031223 [Non-Patent Literature]

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

[Problems to be Solved by the Invention]

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

The inventors have repeatedly conducted active research and found that a compound having a benzothiophene, benzofuran, or indole structure can solve the problem, thereby completing the invention. That is, this invention is as follows.

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

[Chemical 1] (In formula (1), A ¹ and A ² are independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, and pyridine-2,5-diyl. Or naphthalene-2,6-diyl, among these groups, at least one hydrogen may be passed through fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl, difluoromethyl, trifluoromethyl, carbon 1 to 5 alkyl groups, 1 to 5 carbon alkoxy groups, 1 to 5 carbon alkyl esters, or 1 to 5 carbon alkyl groups; Z ¹ and Z ² are each independently 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 have a 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 carbons, or an alkyl group having 1 to 5 carbons; Q ¹ is hydrogen, halogen, or a monovalent organic group; R ¹ and R ² are each independently hydrogen and fluorine , Chlorine, trifluoro Group, trifluoromethoxy group, cyano group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkyl ester having 1 to 20 carbon atoms or formula (2) the group represented;

[Chemical 2] In 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 replaced by -O-, -COO-, -OCO-, -CH = CH-, or -C≡C-; PG is of formula (PG-1) to (PG-8) A polymerizable group represented by any one; * represents a bonding site;

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

[Chemical 4] (In formulas (3) and (4), Z ³ is a single bond, -COO-, or -COS-, respectively; Z ⁴ is 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, 1-20 Alkyl group, -CH ₂ -in the alkyl group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, and hydrogen in the alkyl group may be substituted with halogen; A ^{3 is} independently a bivalent 5-membered ring or 6-membered ring aromatic ring, or their fused ring, A ⁴ is a monovalent 5-membered ring or 6-membered ring aromatic ring, or their fused ring, A At least one hydrogen of the aromatic ring or their condensed ring in ³ and A ⁴ may pass through fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, and carbon. 1 to 5 alkoxy groups, 1 to 5 carbon alkyl esters, 1 to 5 carbon alkyl groups or 1 to 5 thioalkyl groups; p is an integer from 0 to 2) .

[3] The compound according to [1] or [2], wherein at least one of R ¹ and R ² in the formula (1) is a group represented by the formula (2). [4] The compound according to any one of [1] to [3], wherein in 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 1,4-phenylene or 1,4-cyclic ring Hexyl, of these groups, at least one hydrogen may be passed through fluorine, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, or carbon number 1 to 5 alkyl groups; Z ¹ and Z ² are each 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] to [5], wherein in formula (1), Q ¹ is a group represented by formula (4), and in formula (4), Z ⁴ is mono Key, p is an integer of 0 or 1. [7] The compound according to any one of [1] to [6], wherein at least one of A ¹ and A ² in the formula (1) is 1,4-cyclohexyl.

[8] The compound according to any one of [1] to [7], wherein at least one of Z ¹ and Z ² in formula (1) 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] to [8], wherein in the formula (1), R ¹ and R ² are groups represented by the formula (2), and in the formula (2), PG Is a polymerizable group represented by formula (PG-1), and R ⁴ is hydrogen or methyl.

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

[Chemical 5] (In the formulae (4-1) to (4-9), X ² is -O- or -S-, at least one -CH = may be substituted for -N =, and at least one hydrogen may be fluorine, chlorine, or cyano. , Trifluoroacetamido, trifluoromethyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkyl ester with 1 to 5 carbons, or alkyl with 1 to 5 carbons (Replaced by *).

[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 selected from the group of compounds represented by formula (M1) and formula (M2) At least one

[Chemical 6] (In formula (M1) and formula (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2,5- Diyl, naphthalene-2,6-diyl, fluorenone-2,7-diyl, or fluorene-2,7-diyl, at least one of these groups may be fluorine, chlorine, cyano, hydroxy, Formamyl, trifluoroethenyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons or carbon Substituted by alkyl groups of 1 to 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-; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, and 1 to carbon 20 alkoxy groups or 1 to 20 carbon esters; q is an integer of 1 to 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-).

[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),

[Chemical 7] (In formula (M1), A ^{M is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one of A ^M is 1,4-cyclohexyl. Among these groups, at least one hydrogen Can pass fluorine, chlorine, trifluoroacetamyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkyl ester with 1 to 5 carbons Or substituted with an alkyl group having 1 to 5 carbon atoms; Z ^{M is} each 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, 1-20 Alkyl, alkenyl with 1 to 20 carbons, alkoxy with 1 to 20 carbons or alkyl ester with 1 to 20 carbons; 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-).

[14] The liquid crystal composition according to any one of [11] to [13], further containing at least one chiral compound. [15] The liquid crystal composition according to any one of [11] to [14], further containing at least one dichroic pigment 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 including the optically anisotropic film according to [17]. [19] A display element including the optically anisotropic film according to [17]. [20] A display element including the polarizing plate according to [18]. [Effect of the invention]

The compound represented by the formula (1) of the present invention is provided alone or in combination with other known liquid crystal compounds or several kinds of compositions containing these liquid crystal compounds and is uniformly aligned in an arbitrary form, thereby providing each material with a reduced refractive index. Anisotropic wavelength-dependent materials, or materials exhibiting inverse wavelength dispersibility as described above. Furthermore, this liquid crystal composition exhibits a good liquid crystal phase at a relatively low temperature, and exhibits excellent properties such as good solubility in organic solvents. In addition, the polymer obtained by polymerizing the liquid crystal composition of the present invention and a film containing the polymer are not only excellent in the effect of the wavelength dependency, but also have optical anisotropy, transparency, heat resistance, and adhesion. , Excellent 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 circular polarizing element, an elliptical polarizing element, a color compensation film, and a viewing angle compensation film.

The terms used in this specification are described below. First, the meaning of the term "liquid crystallinity" is not limited to having a liquid crystal phase. That is, the liquid crystal compound is a general term for a compound having a liquid crystal phase and a compound which does not have a liquid crystal phase but is useful as a component of a liquid crystal composition. The liquid crystal phase is equal to the nematic phase, the dish phase, and the cholesteric phase, and in most cases is the nematic phase. The lower limit temperature of the liquid crystal is the lower limit temperature at which the liquid crystal phase is displayed, and is the temperature at which the liquid crystal phase transitions to crystals. Polymerizability refers to the ability to provide a polymer by performing monolithic polymerization using methods such as light, heat, and catalyst. The liquid crystal compound having a polymerizable group in the liquid crystal compound is sometimes referred to as a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is included in the liquid crystal compound. The polymerizable compound refers to a compound having a polymerizable group that does not exhibit liquid crystallinity. The case where a compound has one polymerizable group is sometimes called a monofunctional or monofunctional compound. When the compound has a plurality of polymerizable groups, it may be referred to by a polyfunctional or a term corresponding to the number of polymerizable groups. The compound represented by formula (1) may be expressed as compound (1). The compounds represented by other formulas are sometimes referred to by the same simplified method.

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

For example, Y ² in the formula (2) is an alkylene group having 1 to 20 carbon atoms. At least one of the alkylene groups -CH ₂ -may be substituted with -O-, etc., but in this case, it includes the use of The carbon number of the substituted alkylene group such as -O- will not exceed 20. This rule is the same for other definitions.

<< Compound >> The compound represented by general formula (1) is used for the purpose of the wavelength dispersion control of refractive index anisotropy which is the effect of this invention. In this case, one kind may be selected from the compounds represented by these general formula (1), and two or more kinds may be selected and used.

The liquid crystal compound generally 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 including an alkyl group or the like is bonded to the core skeleton. The compound of the present invention has a structure of formula (1) having a benzothiophene, benzofuran or indole structure as the core skeleton.

[Chemical 8] In the formula (1), A ¹ and A ² are independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, and pyridine-2,5-diyl. , Or naphthalene-2,6-diyl. Here, in a case where n and m are 2 or more, the A ¹ and A ² may be different in each iteration. In order to impart high liquid crystallinity to the compound and to have good miscibility with other liquid crystal compounds and organic solvents, A ¹ or A ² are each independently preferably 1,4-phenylene and 1,4-phenylene. cyclohexyl group, in order to make the wavelength dispersion of refractive index anisotropy decreased or vice versa, and more preferably a ¹ or a ² is at least one 1,4-cyclohexylene group. In addition, in the 1,4-phenylene and 1,4-cyclohexyl groups, at least one hydrogen may pass through fluorine, chlorine, cyano, hydroxy, formamyl, trifluoroacetamyl, difluoromethyl, Fluoromethyl, 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 alkyl fluorenyl group having 1 to 5 carbon atoms is substituted. However, in order to impart high liquid crystallinity to a compound and manufacture the compound inexpensively, the substituent of hydrogen is particularly preferably fluorine, trifluoromethyl, alkyl having 1 to 5 carbons, and alkyl having 1 to 5 carbons. An oxygen group, an alkyl ester having 1 to 5 carbon atoms, or an alkyl fluorenyl group having 1 to 5 carbon atoms.

In 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, when n and m are 2 or more, the Z ¹ and Z ² may be different in each repetition thereof. In order to impart high liquid crystallinity to the compound, it has good miscibility with other liquid crystal compounds and organic solvents, and the compound is produced inexpensively. 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- . Furthermore, considering 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- .

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

In Formula (1), X ¹ is -O-, -S-, or -NR ^3- , and R ³ is hydrogen, an alkyl group having 1 to 5 carbon atoms, and an alkyl fluorenyl group having 1 to 5 carbon atoms. In order to have good miscibility with other liquid crystal compounds and organic solvents, and to reduce or reverse the wavelength dispersion of the refractive index anisotropy, X ^{1 is} preferably -S-.

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

[Chemical 9] In 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, the alkylene group Any -CH ₂ -can be replaced by -O-, -COO-, -OCO-, -CH = CH-, or -C≡C-; PG is formula (PG-1) to formula (PG-8) A polymerizable group represented by any of the above. * Indicates a bonding site.

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

Regarding the group represented by R ¹ or R ² , when the present technology is applied to a film application, 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 formulae (PG-1) to (PG-8) can be appropriately selected according to the production conditions of the film. However, when a film is produced by commonly used photo-hardening, the selective formula (PG-) is preferable in terms of high hardenability, solubility in a solvent, low crystallinity, and difficulty in generating alignment defects. 1) Acrylic or methacrylic group represented by

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

[Chemical 11] (In formulas (3) and (4), Z ^{3 is} each independently a single bond, -COO- or -COS-; Z ^{4 is} each 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, 1-20 Alkyl group, -CH ₂ -in the alkyl group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, and hydrogen in the alkyl group may be substituted with halogen; A ^{3 is} independently a bivalent 5-membered ring or 6-membered ring aromatic ring, or their fused ring, A ⁴ is a monovalent 5-membered ring or 6-membered ring aromatic ring, or their fused ring, A At least one hydrogen of the aromatic ring or its condensed ring in ³ and A ⁴ may pass through fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl group 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 alkyl fluorenyl group having 1 to 5 carbon atoms or the thioalkyl group having 1 to 5 carbon atoms are substituted; p is an integer of 0 to 2;

Among the groups represented by Q ¹ , in order to reduce or reverse the wavelength dispersion of the refractive index anisotropy, the group represented by the formula (4) is more preferable, and in order to impart high liquid crystallinity to the compound, It has good miscibility with other liquid crystal compounds and organic solvents, and Q ^{1 is} particularly preferably selected from the groups represented by the formulae (4-1) to (4-9).

[Chemical 12] In formulae (4-1) to (4-9), X ² is -O- or -S-, at least one -CH = may be substituted for -N =, and at least one hydrogen may be fluorine, chlorine, cyano, Trifluoroacetamido, trifluoromethyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkyl ester with 1 to 5 carbons, or alkyl with 1 to 5 carbons To replace. * Indicates a bonding site.

Among the compounds represented by the formula (1), in terms of exhibiting good liquid crystallinity, low transparent point, high solubility in organic solvents, and high compatibility with other compounds, the following are preferred. 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).

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 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 having 1 to 20 carbon atoms, 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 formula (2).

[Chemical 19] In 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, the alkylene group At least one of -CH ₂ -may be replaced by -O-, -COO-, -OCO-, -CH = CH-, or -C≡C-; PG is formula (PG-1) to formula (PG-8) A polymerizable group represented by any of the above.

[Chemical 20] In Formulas (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 carbons, and an alkyl group having 1 to 5 carbons; R ⁵ is hydrogen, fluorine, chlorine, cyano, or an alkyl group having 1 to 20 carbons; CH ₂ -can be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, the hydrogen in the alkyl group can be replaced by halogen, R ⁶ is hydrogen, fluorine, chlorine , Cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, carbon 1 Alkyl group of 5 or thioalkyl group of 1 to 5 carbons.

The compound represented by the formula (1) of the present invention can be synthesized by combining known organic synthetic chemistry methods. The method of introducing the target terminal group, ring and bonding group into the 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 (Organic Reactions) , Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Lecture (Maruzen). The structure of the synthesized compound can be confirmed by, for example, a proton nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrum.

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

As a constituent component other than the compound (1), other liquid crystal compounds (excluding polymerizable liquid crystal compounds), other polymerizable liquid crystal compounds, surfactants, and other polymerizable properties may be contained within a range that does not impair the effects of the present invention. Compounds (except polymerizable liquid crystal compounds), polymerization initiators, light sensitizers, chain transfer agents, antioxidants, ultraviolet absorbers, radical scavengers, light stabilizers, optically active compounds, silane coupling agents, solvents , And other additives.

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

[Chemical 21] In formula (LC), A ^{5 is} independently any one selected from 1,4-phenylene, 1,4-cyclohexyl, pyridine-2,5-diyl, and naphthalene-2,6-diyl Divalent radical, in which at least one hydrogen can pass through fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl, difluoromethyl, trifluoromethyl, carbon number 1 to 5 Substituted by alkyl group, alkoxy group having 1 to 5 carbon atoms, alkyl ester having 1 to 5 carbon atoms or alkyl fluorenyl group having 1 to 5 carbon atoms; Z ^{5 is} independently a single bond or has 1 to 20 carbon atoms At least one of the alkylene groups -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C -Substituted, at least one hydrogen may be replaced by halogen; b is an integer of 1 to 5; R ^{8 is} independently hydrogen, fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl, 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. At least one of the alkyl groups -CH ₂ -may be substituted by -CH = CH-.

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

[Chemical 22]

[Chemical 23]

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

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

[Chemical 25] In formula (M1) and formula (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2,5-di Group, naphthalene-2,6-diyl group or fluorene-2,7-diyl group, at least one of these groups may be fluorine, chlorine, cyano, hydroxy, formamyl, trifluoroethenyl, di Fluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbons; 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 carbons, alkenyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons or 1 to 20 carbons Alkyl ester; q is an integer of 1 to 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, when q is 2 or more, the A ^M and Z ^M may be different in each iteration. Among the compounds represented by the formula (M1) and the formula (M2), the compound represented by the formula (M1) is more preferable, and the compound represented by the formula (M1) is preferably as follows: A ^{M is} independently 1,4-phenylene or 1,4-cyclohexyl, at least one of A ^M is 1,4-cyclohexyl, and at least one of the 1,4-phenylene or 1,4-cyclohexyl Hydrogen can pass through fluorine, chlorine, trifluoroacetamido, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, and alkyl having 1 to 5 carbons Substituted by an ester or an alkyl group having 1 to 5 carbon atoms; Z ^{M is} each 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 Alkyl group, alkenyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or alkyl ester having 1 to 20 carbon atoms; a is an integer of 0 to 20; R ^M is hydrogen or methyl group; Y ^M is a single bond, -O-, -COO-, -OCO-, or -OCOO-.

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

[Chemical 26] In formula (M3), A and ^M are each independently 1,4-phenylene or 1,4-cyclohexyl. Among these groups, at least one hydrogen may be passed through fluorine, chlorine, cyano, hydroxyl, and methylamino. , Trifluoroacetamyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, or 1 to 5 carbons 5 alkyl groups; 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 integers of 0 to 3, and have a 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, when c and d are 2 or more, the A ^M and Z ^M may be different in each iteration.

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 of the liquid crystal composition. A compound having 1,4-cyclohexyl group on at least one of A ^M is more It is easy to control the wavelength dispersion characteristics and the temperature range of the liquid crystal phase. The compound represented by the formula (M2) is a difunctional polymerizable liquid crystal compound, and the polymer has a three-dimensional structure, and therefore is a harder polymer than the compound represented by the formula (M1) having one polymerizable group. The compound represented by formula (M3) is a trifunctional polymerizable liquid crystal compound, and the polymer can further form a strong network and become a harder polymer than a compound having one or two polymerizable groups. Hereinafter, the compound represented by Formula (M1), Formula (M2), and Formula (M3) or a compound derived from these compounds may be collectively referred to as Formula (M).

Hereinafter, preferable examples of the compound represented by the formula (M1) are shown.

[Chemical 27]

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

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

[Chemical 29]

[Chemical 30]

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

Hereinafter, preferable examples of the compound represented by the formula (M3) are shown.

[Chemical 32]

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

A total amount of 100 weight based on at least one compound selected from the compound group of the present invention represented by Formula (1) and at least one compound selected from the compound group represented by Formula (M1) and Formula (M2) %, The polymerizable liquid crystal composition of the present invention preferably contains at least one selected from the group of compounds of the present invention represented by formula (1) in an amount of 10% to 90% by weight. When the content of each of the components in the liquid crystal composition is within the above range, a liquid crystal composition having a wavelength dispersion in which refractive index anisotropy is easily controlled and having a good coatability can be obtained, and further, it can exhibit remarkable performance. The effect of the polymer of the present invention is exhibited.

In addition, 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 contain a surfactant. The surfactant is preferably a nonionic surfactant. When the nonionic surfactant is contained in a liquid crystal composition, it has the effect of improving the smoothness of a coating film containing the liquid crystal composition.

In terms of a weight ratio with respect to the weight of the compound represented by the formula (1), and when it contains other liquid crystal compounds or other polymerizable liquid crystal compounds, it is compared with the compound represented by the formula (1). The weight ratio of the total weight is preferably 0.0001 to 0.5 when a nonionic surfactant is added. A more preferable range of the weight ratio is 0.0001 to 0.005.

Examples of the nonionic surfactant include a silicone-based nonionic surfactant, a fluorine-based nonionic surfactant, and a hydrocarbon-based nonionic surfactant. Commercially available products of the silicone-based nonionic surfactant include, for example, Polyflow ATF- manufactured by Kyoeisha Chemical Co., Ltd., which contains unmodified silicone or modified silicone as a main component. 2.Glanol 100, Glanol 115, Glanol 400, Glanol 410, Glanol 435, Glanol 440, Glanol 450 , Glano 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.

Examples of commercially available products of fluorine-based nonionic surfactants include BYK-340, Ftergent 251, Ftergent 221MH, Ftergent 250, FTX-215M, and 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.

Commercially available products of hydrocarbon-based nonionic surfactants include, for example, Polyflow No. 3, Polyflow No. 50EHF, and Polypropylene containing acrylic polymers as main components. 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-Silclean 3700.

In addition, any one of Polyflow and Glano is the name of a product sold by Kyoeisha Chemical Co., Ltd. BYK is the name of a product sold by BYK-Chemie Japan (stock). Ftergent, FTX and KB are the names of the products sold by Neos.

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

Examples of other polymerizable compounds include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, oxetane derivatives, oxetane derivatives, sorbic acid derivatives, and fumarate Compounds such as acid derivatives and itaconic acid derivatives that do not have liquid crystallinity. Examples of the other polymerizable compound having no liquid crystallinity include a compound having one polymerizable group, a compound having two polymerizable groups, and a polyfunctional compound having three or more polymerizable groups.

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

Examples of the compound having one polymerizable group include styrene, core-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 acids (examples: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), (meth) acrylic acid alkanes Ester (carbon number of alkyl group 1 to 18), hydroxyalkyl ester of (meth) acrylic acid (carbon number of hydroxyalkyl group 1 to 18), amino alkyl ester of (meth) acrylic acid (amino alkyl group) Carbon number of the group is 1 to 18), (meth) acrylic acid-containing alkyl ester containing ether oxygen (carbon number of the ether oxygen-containing alkyl group is 3 to 18, examples: methoxyethyl, ethoxyethyl, Methoxypropyl, 2- (2-methylethyl) ethyl, 2- (2-ethylethyl) ethyl, and 2- (2-butylethyl) ethyl), N-ethylene Acetylamine, vinyl p-tert-butylbenzoate, N, N-dimethylaminobenzoate, vinyl benzoate, vinyl trimethylacetate, 2,2-dimethylbutyric acid Vinyl ester, vinyl 2,2-dimethylvalerate 2-methyl-2-butyric acid vinyl ester, vinyl propionate, vinyl stearate, 2-ethyl-2-methylbutyric acid vinyl ester, dicyclopentyloxyethyl (meth) acrylate, Isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, (meth) acrylic acid Dicyclopentyl ester, dicyclopentenyl (meth) acrylate, 2-propenyloxyethylsuccinic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-propenyloxyethyl Phthalic acid, 2-propenyloxyethyl-2-hydroxyethyl phthalic acid, 2-acrylic acid oxyethyl phosphate, 2-methacrylic acid oxymethyl phosphate Mono (meth) acrylates or di (meth) acrylates of polyalkylene glycols such as ethyl esters, polyethylene glycols with a degree of polymerization of 1 to 100, polypropylene glycols, copolymers of ethylene oxide and propylene oxide Or polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide, such as those having a degree of polymerization of 1 to 100, terminated by alkyl groups having 1 to 6 carbon atoms. (Meth) acrylates and the like.

Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and neopentyl. Diethylene glycol 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 compounds and the like.

Examples of the compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylol EO-added tri (meth) acrylate. , Tri (meth) acrylfluorenyloxyethyl phosphate, tris ((meth) acrylfluorenyloxyethyl) 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 Modified pentaerythritol penta (meth) acrylate, Viscoat V # 802 (number of functional groups = 8), Viscoat V # 1000 (number of functional groups = average 14), etc. "Viscoat" is a trade name of Osaka Organic Chemical Co., Ltd. Those with a functional group of 16 or more are sold through Boltorn H20 (16-functional), Boltorn H30 (32-functional), Boltor sold by Perstorp Specialty Chemicals. (Boltorn) H40 (64-functional) is obtained by subjecting them to acrylization.

Other polymerizable compounds include polymerizable amidine derivatives having a cardo structure. These compounds are suitable for controlling the alignment direction or further improving the degree of hardening of the polymer. Examples of the polymerizable fluorene derivative having a cardo structure are shown in formulas (α-1) to (α-6).

[Chem 34] Moreover, as another polymerizable compound, the polymerizable compound which has a bisphenol structure is mentioned. These compounds are suitable for assisting the film-forming ability or alignment uniformity of the liquid crystal composition. Examples of the polymerizable bisphenol derivative are shown in formulas (N-1) to (N-6).

[Chemical 35] The other polymerizable compounds may be used alone or in combination of two or more. These compounds may be commercially available products.

In order to optimize the polymerization speed, a polymerization initiator may be added to the liquid crystal composition. Examples of the polymerization initiator include a photo radical initiator. Examples of the photo-radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropane-1-one (Darocure 1173), 1-hydroxycyclohexylphenyl ketone, and 2,2- Dimethoxy-1,2-diphenylethane-1-one (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-one (Irgacure 184), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone), Irgacure 2959, Irgacure 907, Ignacure (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, and Irgacure OXE02. The above-mentioned Darocure and Irgacure are the names of the products sold by BASF Japan.

Examples of the photo-radical polymerization initiator include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine and 2- (p-butoxystyryl) -5-trichloromethyl. -1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, benzophenone / michlerone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture , 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, benzyldimethylketal, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinylpropane-1-one, 2,4-diethylxanthone / p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture, etc. .

In terms of a weight ratio with respect to the weight of the compound represented by the formula (1), and when containing other liquid crystal compounds or other polymerizable liquid crystal compounds, In terms of weight ratio of the total weight, the preferable addition amount of the photo radical polymerization initiator is 0.0001 to 0.20. A more preferable range of this weight ratio is 0.001 to 0.15. A particularly preferable range is 0.01 to 0.15. The photo radical initiator may be used singly or in combination of two or more kinds. These polymerization initiators may be commercially available products.

A sensitizer may be added to these photoradical polymerization initiators and used. Examples of the sensitizer include isopropylthioxanthone, diethylthioxanthone, ethyl-4-dimethylaminobenzoate (Darocure EDB), 2-ethyl Hexyl-4-dimethylaminobenzoate (Darocure EHA), etc. These sensitizers may be used alone or in combination of two or more. These sensitizers may be commercially available products.

In order to control the polymerization reaction rate, mechanical characteristics, 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 decreases, and the length of the polymer chain decreases. 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 kinds. These chain transfer agents may be commercially available products.

Examples of the thiol-based chain transfer agent include dodecanethiol, 2-ethylhexyl-3-mercaptopropionate, and the like as a monofunctional thiol, and trimethylol as a polyfunctional thiol. Propane tris (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1), pentaerythritol tetra (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), etc. "Karenz" is a trade name of Showa Denko Corporation.

Examples of the styrene dimerization system chain transfer agent include 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene, and the like. A polymerization inhibitor may be added to the liquid crystal composition to prevent polymerization from starting during storage. Known polymerization inhibitors can be used, and preferred examples thereof are 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methylene blue, Diphenyl picryl hydrazide (DPPH), phenothiazine, N, N-dimethyl-4-nitrosoaniline and other nitroso compounds, o-hydroxybenzophenone, and 2H-1 Benzothiazine derivatives such as, 3-benzothiazine-2,4 (3H) -dione.

In order to improve the storage stability of the liquid crystal composition, a polymerization inhibitor may be added. When radicals are 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, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor, phenol-based antioxidants, sulfur-based antioxidants, and phosphoric acid-based antioxidants can be used.

In order to further improve the weather resistance of the liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), and an antioxidant may be added. Examples of the ultraviolet absorber include: Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, 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, Tinuvin (Tinuvin) 479, Tinuvin 5236, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Ai Adekastab LA-31, Adekastab 1413, and Adekastab LA-51, etc. “Tinuvin” is the trade name of BASF in Japan, and “Adekastab” is the trade name of ADEKA. These ultraviolet absorbers may be used alone or in combination of two or more. These ultraviolet absorbers may be commercially available products.

Examples of the light stabilizer include: Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, and Tinubin (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, Adikastab ( Adekastab LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, Adekastab LA-87, Cyasorb UV-3346 manufactured by Cytec, and Goodri ch) Goodrite UV-3034 from the company. "Chimassorb" is the trade name of BASF Japan. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may be commercially available products.

Antioxidants include, for example, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, and AO-80 of ADEKA. ) Are sold by Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80, and Eluno sold by BASF Japan 1076, Irganox 1010, Irganox 3114, and Irganox 245, etc. These antioxidants may be used alone or in combination of two or more. These antioxidants may be commercially available products.

In order to control the adhesion to the substrate, etc., a silane coupling agent may be added to the liquid crystal composition. Examples of the silane coupling agent include vinyltrialkoxysilane, 3-isocyanatepropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-Dimethylbutene) -3- (trialkoxysilyl) -1-propaneamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrioxane Oxysilane, 3-propenyloxypropyltrimethoxysilane, 3-methacrylic acidoxypropyltrialkoxysilane, and the like. Further, among the alkoxysilanes, a dialkoxymethylsilane in which one of the alkoxy groups (three) is substituted with a methyl group can also be used as a silane coupling agent. These silane coupling agents may be used alone or in combination of two or more. These silane coupling agents may be commercially available products.

For easy application of the liquid crystal composition of the present invention, a solvent can be used to dilute the liquid crystal composition, or each component of the liquid crystal composition can be dissolved in a solvent to prepare a solution of the liquid crystal composition including the liquid crystal composition and a solvent to apply the liquid Solution. Examples of the solvent include ester solvents, amidine solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, Halogenated aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, acetate solvents, and the like.

The ester-based solvent is preferably an alkyl acetate (for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, Amyl acetate and isoamyl acetate), ethyl trifluoroacetate, alkyl propionates (examples: methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, and propionate Butyl ester), alkyl butyrate (example: methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, and propyl butyrate), dialkyl malonate (example: Diethyl malonate), alkyl glycolates (examples: methyl glycolate and ethyl glycolate), alkyl lactates (examples: methyl lactate, ethyl lactate, isopropyl lactate, N-propyl lactate, butyl lactate and ethylhexyl lactate), glycerol monoacetate, γ-butyrolactone and γ-valerolactone, etc.

The amide-based solvent is preferably N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropylamine, N, N-dimethylformamide, N, N -Diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethyl acetal, N-methylcaprolactam and dimethylimidazolidone Wait.

The alcohol-based solvent is preferably: methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, third butanol, second butanol, butanol, 2-ethylbutanol Alcohol, n-hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-pentanol, hexafluoro-2-propanol, propane 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 formazan Cyclohexanol and the like.

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

Glycol monoalkyl ether solvents are preferably: ethylene glycol monoalkyl ether (example: ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), and diethylene glycol monoalkyl ether (example: diethyl ether) Diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (example: propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (example: dipropylene glycol monomethyl ether), ethylene glycol monoalkane Ether ether acetate (example: ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether acetate (example: diethylene glycol monoethyl ether acetate), triethylene glycol monoalkane Ether ether acetate, propylene glycol monoalkyl ether acetate (example: 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 solvents are: benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, cumene, n-propylbenzene, third butylbenzene, second butyl Benzene, n-butylbenzene and tetralin. Preferred examples of the halogenated aromatic hydrocarbon-based solvent are chlorobenzene and the like. The aliphatic hydrocarbon-based solvent is preferably hexane, heptane, or the like. The halogenated aliphatic hydrocarbon-based solvent is preferably chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene, or the like. The alicyclic hydrocarbon-based solvent is preferably cyclohexane, decalin, or the like.

The ketone-based solvent is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methylpropyl ketone, and the like. Acetate-based solvents are preferably: ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl ethyl acetate, and acetic acid-1-methoxy-2- Propyl ester, etc.

From the viewpoint of the solubility of the liquid crystal compound, it is preferable to use a fluorene-based solvent, an aromatic hydrocarbon-based solvent, and a ketone-based solvent. Taking into account the boiling point of the solvent, it is also preferable to use an ester-based solvent and an alcohol-based solvent together. , Ether solvents, glycol monoalkyl ether solvents. The choice of the solvent is not particularly limited. In the case of using a plastic substrate as a support substrate, in order to prevent deformation of the substrate, it is necessary to lower the drying temperature and prevent the solvent from attacking the substrate. The solvents preferably used in this case are: aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, and glycol monoalkyl ether solvents.

The ratio of the solid content in the solution of the liquid crystal composition is 5 to 70% by weight based on the total weight of the solution. The preferable range of this ratio is 10 to 50 weight%, and the more preferable range is 10 to 40 weight%. These solvents may be used alone or in combination of two or more. These solvents may be commercially available products.

In the following description, a polymer (optically 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 as follows. First, a liquid crystal composition is applied on a support substrate in a fluid state to form a coating film. When a solution of a liquid crystal composition is prepared, it is applied on a support substrate and dried to form a coating film. This coating film was irradiated with light to polymerize the liquid crystal composition, and the composition in the coating film was fixed in a nematic orientation formed in a liquid crystal state. Examples of the material of the supporting substrate include glass and plastic. Examples of plastics include polyimide, polyimide, imine, polyimide, polyetherimide, polyetheretherketone, polyetherketone, polyketosulfide, polyetherimide, polyfluorene, and polyphenylenesulfide. Ether, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol , Polypropylene, cellulose, triethylfluorenyl cellulose and some saponified products thereof, epoxy resin, phenol resin, and cycloolefin resin. The supporting substrate is usually a sheet or a film.

Examples of the cycloolefin-based resin include a norbornene-based resin and a dicyclopentadiene-based resin. However, the resin is not limited to these resins. Among these resins, those having no unsaturated bond or having an unsaturated bond being hydrogenated are suitably used. Examples include: hydrides of ring-opening (co) polymers of one or two or more norbornene-based monomers; addition (co) polymers of one or two or more norbornene-based monomers; Addition copolymers of norbornene-based monomers and olefin-based monomers (α-olefins such as ethylene), norbornene-based monomers and cycloolefin-based monomers (cyclopentene, cyclooctene, 5,6-dihydro Dicyclopentadiene, etc.) addition copolymers, and these modified products, etc., specifically include: ZEONEX, ZEONOR (both trade names, Japanese Swiss ZEON (manufactured by), Arton (trade name, manufactured by JSR), TOPAS (trade name, manufactured by TICONA), Apel ( 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 that can be used as a support substrate may be a uniaxially stretched film or a biaxially stretched film. These films may be, for example, films subjected to a hydrophilization treatment such as a corona treatment or a plasma treatment, or a surface treatment such as a hydrophobic treatment. The method of hydrophilizing treatment is not particularly limited, and it is preferably a corona treatment or a plasma treatment, and a particularly preferred method is a plasma treatment. For the plasma treatment, methods described in Japanese Patent Laid-Open No. 2002-226616, Japanese Patent Laid-Open No. 2002-121648, and the like can be used. In addition, in order to improve the adhesion between the liquid crystal film and the plastic film, an adhesive undercoat layer may be formed. As long as such an undercoat layer improves adhesion between the liquid crystal film and the plastic film, there is no problem even if it is any of an inorganic material and an organic material. In addition, the plastic film may be a laminated film. Instead of plastic film, metal substrates such as aluminum, iron, and copper with slit-shaped grooves on the surface can also be used, or the surface is etched to form slit-shaped glass, borosilicate glass, and flint glass ( flint glass).

When forming a liquid crystal film of parallel alignment and mixed alignment on a supporting substrate such as a glass substrate or a plastic film before forming a coating film of the liquid crystal composition, a physical or mechanical surface treatment by rubbing or the like is performed. In the case of forming a liquid crystal film having a vertical alignment, there are many cases in which surface treatment such as rubbing is not performed, but rubbing treatment may be performed in terms of preventing alignment defects and the like. Any method may be used for the rubbing treatment. Generally, the following method is used: a rubbing cloth containing raw materials such as rayon, cotton, polyamide, etc. is wound on a metal roll, etc., and the roll is brought into contact with a supporting substrate or a polymer film. A method of moving while rotating; a method of moving the support substrate side with the roller fixed. The rubbing treatment may be performed directly on the support substrate, or a polymer coating film such as polyimide generally referred to as an alignment film may be provided on the support substrate in advance, and the polymer coating film may be rubbed. The rubbing method is as described above. Depending on the type of support substrate, silicon oxide may be vapor-deposited obliquely on the surface to provide alignment ability.

In addition, in the case of forming a liquid crystal film having a parallel alignment and a mixed alignment, in addition to performing physical and mechanical surface treatments such as rubbing, a polyimide generally called a photo-alignment film may be provided in advance on a supporting substrate. Or a polymer film such as polyacrylate, and the polymer film is subjected to polarized UV treatment.

Examples of coating methods used to obtain a uniform film thickness when applying a liquid crystal composition or a solution thereof are: spin coating method, micro gravure coating method, gravure coating method, wire rod coating method, dip coating method, Spray coating method, meniscus coat method, and die coating method. In particular, a wire rod coating method such as applying a shear stress to the liquid crystal composition during coating can be used to control the alignment of the liquid crystal composition without performing a 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 the application. For the heat treatment, a hot plate or a drying furnace, hot air or hot air blowing, and the like can be used.

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

The heat treatment of the coating film is preferably performed under conditions to obtain uniform alignment of the polymerizable liquid crystal. It can also be performed 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 to a temperature at which the liquid crystal composition exhibits a nematic liquid crystal phase, and the liquid crystal composition in the coating film is formed into a nematic alignment. It is also possible to form a nematic alignment by changing the temperature of a coating film in the temperature range in which a liquid crystal composition shows a nematic liquid crystal phase. This method is a method in which the nematic alignment is substantially completed in the coating film by warming the coating film to a high temperature region of the temperature range, and then the temperature is further reduced to an orderly alignment. In the case of using any of the heat treatment methods, the heat treatment temperature is from room temperature to 120 ° C. The preferred range of this temperature is from room temperature to 80 ° C, and the more preferred range is from room temperature to 60 ° C. The heat treatment time is 5 seconds to 2 hours. A preferred range of this time is 10 seconds to 40 minutes, and a more preferred range is 20 seconds to 20 minutes. In order to raise the temperature of the layer containing the liquid crystal composition to a predetermined temperature, the heat treatment time is preferably set to 5 seconds or more. In order not to reduce productivity, the heat treatment time is preferably set to within 2 hours. In this way, the polymerizable liquid crystal layer of the present invention was obtained.

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

When 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 various optical elements, or as an optical compensation element used in a liquid crystal display device In the case of application, it is extremely important to control the distribution of the inclination angle in the thickness direction.

One method of controlling the tilt angle is a method of adjusting the type, composition ratio, and the like 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 type of the solvent or the concentration of the solute in the liquid crystal composition, the type or the amount of the surfactant to be added as one of the other components, and the like. The tilt angle of the liquid crystal film may be controlled according to the type or friction conditions of the support substrate or the polymer film, the drying conditions or heat treatment conditions of the coating film of the liquid crystal composition. Furthermore, the irradiation environment and temperature during irradiation in the photopolymerization step after alignment also affect the tilt angle of the liquid crystal film. That is, it is thought that almost all conditions in the manufacturing process of the liquid crystal film will affect the tilt angle to some extent. Therefore, by optimizing the liquid crystal composition and appropriately selecting the conditions of the manufacturing process of the liquid crystal film, it can be set to an arbitrary tilt angle.

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

A chiral compound, that is, a compound having optical activity may be added to the liquid crystal composition of the present invention. Preferable examples of the optically active compound are compounds represented by the formula (Op-1) to (Op-25). In these formulas, Ak represents an alkyl group having 1 to 15 carbon atoms or alkoxy group having 1 to 15 carbon atoms, and Me, Et, and Ph each represent a methyl group, an ethyl group, and a phenyl group. P ² is a polymerizable group, and is preferably a group containing a (meth) acrylfluorenyloxy group, a vinyloxy group, an oxetanyl group, or an oxetanyl group. The liquid crystal composition of the present invention can be used not only as a raw material of a polymer described below, but also as a liquid crystal as a constituent element of a liquid crystal display element.

[Chemical 36]

[Chemical 37] Specific examples include those described in paragraph 0159 on page 70 to paragraph 0170 on page 81 of Japanese Patent Laid-Open No. 2011-148762.

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 is coated on an alignment-treated substrate and polymerized to obtain a spiral structure (twisted). Structure) of retardation film. The helical structure is fixed by the polymerization of the liquid crystal composition. The characteristics of the obtained liquid crystal film depend on the pitch of the obtained helical structure. The pitch length can be adjusted by the type and addition 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 canceling the temperature dependence of the pitch. The liquid crystal composition may contain other polymerizable compounds in addition to the optically active compound.

The characteristics of the liquid crystal film described above, that is, the selective reflection of light is a spiral structure that acts on incident light and reflects circularly or elliptically. The selective reflection characteristic is represented by λ = n · Pitch (λ is the central wavelength of the selective reflection, n is the average refractive index, and Pitch is the pitch), so the [adjust] center wavelength (λ) can be appropriately prepared by changing n or pitch And the wavelength amplitude (Δλ). In order to achieve good color purity, it is only necessary to reduce the wavelength width (Δλ), and when wide-band reflection is required, it is only necessary to increase the wavelength width (Δλ). Furthermore, this selective reflection is also greatly affected by the thickness of the polymer. In order to maintain color purity, the thickness must not become too small. In order to maintain uniform alignment, it is necessary to prevent the thickness from becoming too large. Therefore, an appropriate thickness needs to be adjusted, preferably 0.5 μm to 25 μm, and more preferably 1 μm to 10 μm.

By making the pitch shorter than visible light, it is possible to prepare the material described in WH de Jeu, "Physical Properties of Liquid Crystalline Materials" (Gordon and Breach, New York (1980)) Negative C plate. In order to shorten the pitch, it can be achieved by using an optically active compound having a large torque (HTP: helical twisting power), and then increasing the amount of addition. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, and preferably 200 nm or less. The negative C plate becomes a vertical alignment nematic (VAN) type, a vertical alignment cholesteric (VAC) type, and an optically compensated birefringence (OCB) suitable for liquid crystal display elements. Type optical compensation film for display elements.

The liquid crystal film can be used for a reflection film whose reflection wavelength region is set to near infrared (wavelength of 800 nm to 2500 nm) as described in Japanese Patent Laid-Open No. 2004-333671 by making the pitch longer than visible light. In order to increase the pitch, for example, it is possible to achieve this by using an optically active compound having a small torque or reducing the amount of the optically active compound added.

Any optically active compound can be used as long as the optically active compound can cause a helical structure and is appropriately mixed with the liquid crystal composition to be a raw material. In addition, it may be either a polymerizable compound or a non-polymerizable compound, and an optimum compound may be added depending on the purpose. When considering heat resistance and solvent resistance, a polymerizable compound is preferable.

Furthermore, among the optically active compounds, a larger torque (HTP: helical twisting power) is preferred in terms of shortening the pitch. Representative examples of compounds with high torsion are disclosed in GB2298202 and DE10221751.

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

The higher the birefringence (value of optical anisotropy) of the liquid crystal film, the thinner the thickness. As the thickness is thinner, optical characteristics such as haze value and transmittance tend to be good. The liquid crystal film is effective as an optical compensation element suitable for a liquid crystal display element (especially 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 (Twisted Nematic), STN (Super Twisted Nematic), ECB (Electrically Controlled Birefringence), DAP (Integral Phase Distortion Arrangement Perpendicular), CSH type (Color Super Homeotropic), VAN / VAC type (vertically aligned nematic / cholesteric phase), OMI type (Optical Mode Interference) ), SBE type (Supertwisted Birefringence Effect), etc. Furthermore, this liquid crystal film can also be used as a phase retarder for display elements such as a guest-host type, a ferroelectric type, and an antiferroelectric type. In addition, the optimal values of parameters such as the distribution in the thickness direction and the thickness of the tilt angle required by the liquid crystal film strongly depend on the type of the liquid crystal display element to be compensated and its optical parameters, and therefore vary 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 arranged outside the liquid crystal cell. On the other hand, the liquid crystal film as an optical compensation element can be disposed inside the liquid crystal cell because the elution of impurities into the liquid crystal filled in the cell is absent or small. For example, if the method disclosed in Japanese Patent Laid-Open 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 the color filter. In addition, there is no particular limitation on the type of polarizing plate used in the optical element to which the liquid crystal film can be applied. In addition to the widely used absorbing iodine-type absorbing polarizing plate, it is also suitable for reflective polarization such as wire grid polarizing plates. Optical compensation of the film.

The liquid crystal film may contain additives such as a dichroic dye. The dichroic pigment is preferably a pigment containing anthraquinone, naphthoquinone, or azobenzene. A liquid crystal film with a parallel alignment compounded with a dichroic dye can also be used as an absorption-type polarizer. In addition, a liquid crystal film having a parallel alignment compounded with a fluorescent dye can also be used as a polarized light-emitting film. [Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples. <Confirmation of Compound Structure> The structure of the synthesized compound was confirmed by measurement of 500 MHz proton NMR (Bruker: DRX-500). The numerical values shown are ppm, s is singlet, d is doublet, t is triplet, and m is multimodal.

<Phase transition temperature> A sample was placed on a hot plate provided with a melting point measuring device of a polarization microscope, and the temperature was raised at a rate of 3 ° C / min. The temperature at which a phase transitions to another phase is measured. C refers to crystal, N refers to nematic phase, S refers to dish-like phase, and I refers to isotropic liquid. The NI point is an upper limit temperature of a nematic phase or a transition temperature at which a nematic phase transitions into an isotropic liquid. "C 50 N 63 I" changed from a crystal to a nematic phase at 50 ° C, and changed from a nematic phase to an isotropic liquid at 63 ° C. The parentheses indicate the liquid crystal phase of a single change.

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

<Evaluation of alignment> (1) Production of a glass substrate with a rubbed alignment film On a glass substrate having a thickness of 1.1 mm, polyimide for low pretilt angle (horizontal alignment mode) was spin-coated (Lexit calibration) (LIXON Aligner): PIA-5370 (manufactured by JNC). After removing the solvent from the spin-coated coating film on a 80 ° C hot plate, the coating film was calcined in an oven at 230 ° C for 30 minutes. , The rubbing treatment is performed on the burned man using a rayon cloth.

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

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

<Measurement of film thickness> The layer of the liquid crystal film of the glass substrate with a liquid crystal film was cut out and measured using a fine shape measuring device (manufactured by KLA TENCOR, Inc., Alpha Step IQ). Step difference.

<Evaluation of Optical Anisotropy (Δn)> The optical anisotropy (Δn) was determined based on the retardation and film thickness values when the incident angle of light obtained for a liquid crystal film with parallel alignment was 90 ° with respect to the film surface. = Delay (Re) / Film thickness (d).

<Evaluation of the wavelength dispersion characteristic> As the wavelength dispersion characteristic, the value calculated | required from the following formula was used as an index. Wavelength dispersion characteristics = retardation measured with 450 nm light (Re _{450 nm} ) / retardation measured with 550 nm light (Re _{550 nm} ). That is, the lower the wavelength dispersion characteristic value is, the lower the wavelength dispersion property is, and when the value is 1 or less, it indicates that it has the reverse wavelength dispersion characteristic.

<Pencil hardness> It measured according to the method of JIS standard "JIS-K-5400 8.4 pencil scratch test". That is, using a pencil hardness tester (C-221 manufactured by Yoshimitsu Seiki), the scratches of the pencil at the time of the scratch were measured on the scratches obtained using a core of a pencil (Mitsubishi Pencil (Strand) Uni) fixed at an angle of 45 °. Core hardness.

[Example 1] The following compound (1-1-2-1) was synthesized as follows.

[Chemical 38] The compound (ex-1) was synthesized based on 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 stirred at 10 degreeC or less for 3 hours. 160 mL of 1N hydrochloric acid water was added to the reaction solution, followed by 160 mL of water. The precipitate was separated by filtration and washed with a large amount of water, thereby obtaining 15.5 g of a compound (ex-2).

Add 5.0 g of compound (ex-2), 9.3 g of 4-pentylcyclohexanecarboxylic acid, and 1.1 g of 4-dimethylaminopyridine (DMAP) to 90 ml of dichloride Stir in methane while cooling in a nitrogen atmosphere. 20 mL of a dichloromethane solution of 9.7 g of 1,3-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene) and recrystallized from methanol to obtain 8.2 g of the 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 95 I ¹ H-NMR (CDCl ₃ ; δppm): 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 following compound (1-1-19-1) was synthesized as follows.

[Chemical 39] The compound (ex-3) was synthesized according to 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 in a nitrogen atmosphere. 10 mL of 4.5 g of a DCC solution in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene) and recrystallized from methanol to obtain 4.8 g of a compound (ex -4).

4.8 g of the compound (ex-4) was added to 150 mL of acetonitrile (MeCN), and the mixture was stirred at room temperature under a nitrogen atmosphere. 45 mL of an aqueous solution of 17.6 g of cerium (IV) ammonium nitrate (CAN) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Toluene and water were added to extract the organic layer, 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 a mixed solution of toluene and methanol to obtain 4.2 g of a compound (ex-5).

4.2 g of 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 stirred at 10 degreeC or less for 3 hours. 40 mL of 1N hydrochloric acid water was added to the reaction solution, followed by 40 mL of water. The precipitate was separated by filtration and washed with a large amount of water to obtain 4.0 g of a compound (ex-6).

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 methylene chloride, and the mixture was stirred while cooling under a nitrogen atmosphere. 10 mL of a 3.0 m solution of DCC in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene) and recrystallized from methanol to obtain 4.9 g of the 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 110 I ¹ H-NMR (CDCl ₃ ; δppm): 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 as follows.

[Chemical 40] Compound (ex-7) was synthesized based on Heterocyclic communications. 8, 2, 135 (2002). 5.0 g of 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 Stir for 4 hours while heating at 100 ° C in an environment. Water was poured into the reaction solution, 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, thereby obtaining 3.5 g of a compound (ex-8).

3.0 g of the compound (ex-8) was added to 90 mL of acetonitrile (MeCN), and the mixture was stirred at room temperature under a nitrogen atmosphere. 18 mL of a 12.8 g CAN aqueous solution was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Toluene and water were added to extract the organic layer, 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 a mixed solution of toluene and methanol to obtain 1.4 g of a compound (ex-9).

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. To this was added 0.5 g of sodium borohydride. Then, it stirred at 10 degreeC or less for 3 hours. 14 mL of 1N hydrochloric acid water was added to the reaction solution, followed by 14 mL of water. The precipitate was separated by filtration and washed with a large amount of water to obtain 1.0 g of a compound (ex-10).

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 at reflux under a nitrogen atmosphere for 6 hours. 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, thereby obtaining 24.4 g of a compound (ex-11).

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 10 ° C in a nitrogen atmosphere. 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 sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure, and the residue was subjected to column chromatography (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 2/1)) The purified product was dried under reduced pressure to obtain 25.2 g of a compound (ex-12).

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 stirred while cooling in a nitrogen atmosphere. 50 mL of a dichloromethane solution of 22.9 g of DCC was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) Purification was performed to obtain 34.3 g of a compound (ex-13).

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 in an autoclave under a hydrogen atmosphere at room temperature for 24 hours. The insoluble matter was separated by filtration and ethanol was distilled off under reduced pressure to obtain 25.2 g of a compound (ex-14).

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 under cooling in a nitrogen environment at 10 ° C or lower. To this was slowly added 8.3 g of propylene chloride. After the dropwise addition, the mixture was stirred at room temperature for 8 hours. Water was added to extract the organic layer, and the organic layer was washed with saturated sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 14/1)) Purified 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 saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of ethyl acetate and heptane to obtain 7.4 g of a compound (ex-15).

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 methylene chloride, and the mixture was stirred while cooling in a nitrogen atmosphere. 11 mL of a 5.1 g solution of DCC in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) Purification was performed and recrystallization was performed in methanol, whereby 3.6 g of a 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 as follows.

[Chemical 41] 50.0 g of 4-hydroxybutyl acrylate and 50 mL of pyridine were added to 150 mL of toluene, and the mixture was stirred at room temperature under a nitrogen atmosphere. 72.8 g of tosylsulfonium chloride was slowly added thereto. Then, it stirred at room temperature for 16 hours. Furthermore, water was added, and it heat-stirred at 40 degreeC for 3 hours. The organic layer was extracted, washed with 5% hydrochloric acid water and saturated sodium bicarbonate water, then washed with water, dried over anhydrous magnesium sulfate, and toluene was distilled off 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 heated and stirred 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 sodium bicarbonate water and water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was subjected to column chromatography (silica dioxide, eluent: A toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1) was purified to obtain 22.9 g of a compound (ex-16).

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 heated and stirred 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. Toluene and 3N hydrochloric acid water were added to extract the organic layer. 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 a 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 at 10 ° C or lower under a nitrogen atmosphere. 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 to extract the organic layer, and the organic layer was washed with saturated sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. The toluene was distilled off under reduced pressure, and the residue was purified by column chromatography (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)). 32.4 g of compound (ex-18) was obtained by drying under reduced pressure.

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 in a hydrogen atmosphere at room temperature for 24 hours using an autoclave. Insoluble matter was separated by filtration, THF was distilled off under reduced pressure, chloroform was added, and crystals were separated by filtration to obtain 7.1 g of a 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 methylene chloride, and the mixture was stirred while cooling under a nitrogen atmosphere. 15 mL of a 7.0 m solution of DCC in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) Purified 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 heated and stirred at 40 ° C for 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of ethyl acetate and heptane to obtain 3.3 g of a compound (ex-20).

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 in a nitrogen atmosphere. . 5 mL of 1.8 g of a DCC solution in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) Purification was performed, and recrystallization was performed in methanol, whereby 1.8 g of a 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" has the following meanings: Although polymerization cannot be performed at temperatures near 180 ° C, it is expected to exist above 180 ° C if polymerization is not performed. Transition temperature from nematic to isotropic liquid) 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 following compound (1-1-6-1) was synthesized as follows.

[Chemical 42] 50.0 g of 6-chlorohexanol, 66.0 g of 3- (4-hydroxyphenylpropionic acid methyl ester), 49.2 g of potassium carbonate, and 6.1 g of potassium iodide were added to 330 mL of DMF under a nitrogen atmosphere. Heat and stir at 80 ° C for 10 hours. Toluene and water were added to extract the organic layer. The organic layer was washed with saturated sodium bicarbonate water and water, dried over anhydrous magnesium sulfate, and toluene was distilled off 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 stirred under reflux in a nitrogen atmosphere for 3 hours. The methanol was distilled off under reduced pressure, ethyl acetate and 3N hydrochloric acid water were added, and the organic layer was extracted. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was recrystallized from a mixed solution of toluene and ethanol to obtain 69.2 g of a 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 stirred under a nitrogen atmosphere at 10 ° C or lower while cooling. 28.2 g of propylene chloride was slowly added dropwise thereto. After the dropwise addition, the mixture was heated and stirred at 40 ° C for 4 hours. Water was added to extract the organic layer, 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 to obtain 50.0 g of a compound (ex-22).

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 in a nitrogen atmosphere. . 60 mL of a dichloromethane solution of 29.0 g of DCC was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate was separated by filtration, and the organic layer was washed with saturated sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was subjected to column chromatography (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 12/1)) Purified 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 heated and stirred at 40 ° C. for 8 hours. Ethyl acetate and water were added, and the organic layer was extracted. The organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of ethyl acetate and heptane to obtain 31.8 g of a 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 in a nitrogen atmosphere. . 12 mL of a 5.9 g solution of DCC in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) Purification was performed, and recrystallization was performed in methanol, whereby 10.7 g of a 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 ; δppm): 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] A 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).

[Chemical 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 ; δppm): 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 as follows.

[Chemical 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 thionyl chloride, and the mixture was stirred under reflux in a nitrogen atmosphere for 1 hour. Dithionine chloride was distilled off under reduced pressure, and 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. To this was added 2.6 g of 2-aminobenzenethiol dropwise. After the dropwise addition, the mixture was stirred at 10 ° C. or lower for 1 hour, and 2.3 g of triethylamine was further 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 sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. THF and ethyl acetate were distilled off under reduced pressure, and the residue was subjected to column chromatography (silica dioxide, eluent: toluene-dichloromethane mixture (volume ratio: toluene / dichloromethane = 2/1) )) Purified and dried under reduced pressure to obtain 1.2 g of compound (ex-24).

1.2 g of compound (ex-24) was added to 24 mL of acetonitrile (MeCN), and the mixture was stirred at room temperature under a nitrogen atmosphere. 10 mL of an aqueous 4.2 g CAN solution was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 4 hours. Dichloromethane and water were added to extract the organic layer, and 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 a 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 stirred at 10 degreeC or less for 3 hours. 10 mL of 1N hydrochloric acid water was added to the reaction solution, followed by 10 mL of water. The precipitate was separated by filtration and washed with a large amount of water to obtain 0.9 g of a compound (ex-26).

0.9 g of compound (ex-26), 2.8 g of compound (ex-23) described in Example 5, and 0.2 g of DMAP were added to 30 mL of dichloromethane, and stirred while cooling in a nitrogen atmosphere. . 5 mL of 1.3 g of a DCC solution in methylene chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) Purification was performed, and recrystallization was performed in methanol, whereby 1.0 g of a 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 ; δppm): 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 following compound (1-1-20-1) was synthesized as follows.

[Chemical 45] 8.0 g of 4-bromomethylbiphenyl and 9.8 g of potassium carbonate were added to 40 ml of THF, and the mixture was stirred at room temperature under a nitrogen atmosphere. To this was added dropwise 3.0 g of thioacetic acid. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 40 ml of MeOH was added to the reaction solution, and the mixture was further stirred for 1 hour. The solution was neutralized by dropwise addition of a 3N aqueous hydrochloric acid solution, and ethyl acetate was added for extraction. Furthermore, the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 6.4 g of a 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) under a nitrogen atmosphere. The mixture was stirred at 60 ° C for 4 hours while heating. 1.6 g of potassium hydroxide was added thereto, and the mixture was stirred at 100 ° C for 1 hour. Water was poured into the reaction solution, 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, thereby obtaining 2.4 g of a compound (ex-28).

2.0 g of compound (ex-28) was added to 60 mL of acetonitrile (MeCN), and the mixture was stirred at room temperature under a nitrogen atmosphere. To this, 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. Dichloromethane 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, thereby obtaining 1.3 g of a compound (ex-29).

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 stirred at 10 degreeC or less for 3 hours. To the reaction solution, 13 mL of 1N hydrochloric acid water was added, followed by 13 mL of water. The precipitate was separated by filtration and washed with a large amount of water to obtain 1.3 g of a compound (ex-30).

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 while cooling in a nitrogen environment. 4 mL of a dichloromethane solution of 1.8 g of N, N'-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) Purification was performed and recrystallization was performed in methanol, whereby 1.6 g of a 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 103 I ¹ H-NMR (CDCl ₃ ; δppm): 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] A compound shown below 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).

[Chemical 46]

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-3) are as follows. Phase transition temperature (℃): C 109 I ¹ H-NMR (CDCl ₃ ; δppm): 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] A compound shown below was synthesized by the same method except that 4-bromomethylbiphenyl was changed to 4-trifluoromethylbenzyl bromide in the synthesis method described in Example 8. -1-6-4).

[Chemical 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 ; δppm): 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 as follows.

[Chemical 48] 5.0 g of compound (ex-3), 2.9 g of benzamidine hydrazine, and 0.5 g of N, N-dimethyl-4-aminopyridine (DMAP) were added to 100 mL of dichloromethane. Stir while cooling under a nitrogen atmosphere. 8 mL of a dichloromethane solution of 4.4 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. Water was added to the reaction solution, and the crystals were separated by filtration. The obtained crystals were washed with water and dichloromethane to obtain 5.4 g of a 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 the mixture was stirred at room temperature under a nitrogen atmosphere. To this was added 11.3 g of potassium tosylsulfonium chloride (TsCl) hydroxide, and the mixture was stirred at room temperature for 16 hours. The crystals were separated by filtration, and the obtained crystals were washed with water and methanol to obtain 4.8 g of a compound (ex-32).

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. 6.2 g of boron tribromide was added dropwise thereto. After the dropwise addition, the mixture was stirred at -70 ° C or lower for 2 hours and then at room temperature for 8 hours. The reaction solution 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 while cooling in a nitrogen environment. 5 mL of a dichloromethane solution of 2.4 g of N, N'-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The deposited precipitate 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 (silica dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) Purification was performed, and recrystallization was performed in methanol, whereby 3.2 g of a 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 ; δppm): 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 a liquid crystal composition> [Example 12] The compound of the present invention synthesized as described above was used with the compound (M2-7-1), compound (M1-15-1), and compound (M1-16-1) shown below. ) And compound (M1-17-1) to prepare a liquid crystal composition (S-1 to S-12).

[Chemical 48] The types and contents of the compound of the present invention in the liquid crystal composition, the types and contents of other polymerizable liquid crystal compounds, 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 percentage of each material when the total weight of the liquid crystal composition is 100% by weight. Irgacure 907 (manufactured by BASF) was used as the polymerization initiator, Ftergent FTX-218 (neos) was used as the surfactant, and the solvent was used. A mixed solution of cyclopentanone and toluene was used (the mixing ratio of cyclopentanone-toluene was 1/1 by weight ratio).

[Table 1]

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

[Comparative Example 1] In the same manner as the method described in Example 12, the compound (M2-7-1), the compound (M1-15-1), and the compound (M1-16-1) were used with the following Compound (C-1) to prepare a liquid crystal composition (SC-1 to SC-3).

[Chemical 49]

[table 3]

<Production of Optical Anisotropic Film> [Example 14] The liquid crystal composition (S-1) to the liquid crystal composition (S-12) produced in Examples 12 and 13 were applied to a tape by spin coating. On the glass substrate with the rubbing-treated alignment film. The substrate was heated at 80 ° C. for 2 minutes, and cooled at room temperature for 1 minute. The polymerizable liquid crystal layer from which the solvent was removed was polymerized in the air using ultraviolet rays to obtain an optically anisotropic film that fixed the alignment state of the liquid crystal. . The obtained optically anisotropic film was confirmed with a polarization microscope observation and a polarization analysis device. As a result, there were no alignment defects and uniform parallel alignment was obtained.

[Comparative Example 2] In the same manner as the method described in Example 14, 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. The obtained optically anisotropic films were confirmed with a polarization microscope observation and a polarization analysis device. As a result, it was confirmed that (SC-1) and (SC-2) have no alignment defects and have uniform parallel alignment; ( SC-3) Crystals were precipitated, alignment defects were generated, and a film with uniform parallel alignment was not obtained.

If (SC-3) is compared with (S-6), it can be seen that if the liquid crystal compound (1) of the present invention is used, it is possible to form uniform parallel lines that are difficult to form when only the compound (C-1) is used. Aligned film.

<Optical characteristics of optically anisotropic film> [Example 15 to Example 26, Comparative Example 3 to Comparative Example 4] The film surface of the optically anisotropic film produced in Example 14 and Comparative Example 2 was Tables 4 and 5 show the measured values of the 90-degree retardation at a wavelength of 450 nm (Re ₄₅₀ ), the measured values of the wavelength 550 nm (Re ₅₅₀ ), the film thickness, Δn at a wavelength of 550 nm, and the wavelength dispersion characteristics.

[Table 4]

[table 5]

The optically anisotropic films of Examples 15 to 26 showed lower values of the wavelength dispersion characteristics than those of Comparative Example 3. This supports the fact that by incorporating the compound of the present invention into a liquid crystal composition, there is an effect of reducing the wavelength dispersion characteristic, and it is understood that the wavelength dispersion characteristic of the optically anisotropic film obtained can be controlled by using the compound of the present invention . In addition, in the optically anisotropic film of Example 20, the wavelength dispersion characteristic showed a value of 1 or less, and it was confirmed that it has a reverse wavelength dispersion characteristic.

<The heat resistance of the optical characteristics of the optically anisotropic film> The following results are shown in Tables 6 and 7, and the results are shown in Tables 2 and 3 relative to the optically anisotropic films produced in Example 14 and Comparative Example 2. After the film surface was calcined at 30 ° C for 30 minutes, the measurement was performed at a wavelength of 550 nm with a retardation of 90 degrees. Here, in Tables 6 and 7, the residual Re means the value of Re after the initial Re value was set to 100 and then calcined at 200 ° C for 30 minutes.

[TABLE 6]

[TABLE 7]

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

<Mechanical characteristics of optically anisotropic film> Table 8 and Table 9 show 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 a pencil hardness test. Here, in Tables 8 and 9, hardness (parallel) indicates the hardness of the core of a pencil when a scratch occurs when a scratch is made in a direction parallel to the alignment direction of the optically anisotropic film, and the hardness (vertical ) Indicates the hardness of the core of the pencil when a scratch occurs when a scratch is made in a direction perpendicular to the alignment direction of the optically anisotropic film.

[TABLE 8]

[TABLE 9]

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

[Chemical 50] These compounds were mixed at a weight ratio of compound (1-1-6-1): compound (M2-1-1): compound (M1-12-1) = 33: 33: 34. Let this composition be MIX1. To this MIX1, GA-1000 (manufactured by Osaka Gas Chemical Co., Ltd.) with a weight ratio of 0.10 and polymerization initiator Irgacure 907 (manufactured by BASF, Japan) with a weight ratio of 0.06 are added, Cyclohexanone was further added to prepare a liquid crystal composition (S-13) with a solvent ratio of 75% by weight.

<Production of Optical Anisotropic Film> [Example 28] The liquid crystal composition (S-13) produced in Example 27 was applied to a glass substrate (slide glass) by spin coating: S- 1112) on. 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 using 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 with a retardation of 45 degrees in the slow axis direction with respect to the film surface of the optically anisotropic film produced in Example 28 The value (Re ₄₅₀ ) and the measured value (Re ₅₅₀ ) at a wavelength of 550 nm were 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. The liquid crystal composition using the compound is easy to control the wavelength dispersion characteristics, and Since the compatibility and solubility are excellent, an optically anisotropic film can be easily obtained. In addition, the obtained optically anisotropic film has high mechanical strength or heat resistance. Therefore, a film containing the polymer is suitable for, for example, a retardation film, an optical compensation film, a reflection film, a selective reflection film, an anti-reflection film, a viewing angle compensation film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, and elliptical polarization Elements and the like, and display elements having these films or elements.

no

no

Claims (17)

A liquid crystal compound, which is a compound represented by formula (1): In Formula (1), A ¹ and A ² are each independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2,5-diyl, Or naphthalene-2,6-diyl, among these groups, at least one hydrogen may be passed through fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl, difluoromethyl, trifluoromethyl, carbon 1 to 5 alkyl groups, 1 to 5 carbon alkoxy groups, 1 to 5 alkyl esters or 1 to 5 carbon alkyl groups; Z ¹ and Z ² are each independently 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 ~ 3, and have a relationship of 1 ≦ m + n ≦ 4; X ¹ is -S-; Q ¹ is represented by formula (4) Represented groups; In formula (4), Z ³ is a single bond, -COO-, or -COS-; Z ⁴ is a single bond, and A ^{3 is} each independently a divalent 5- or 6-membered aromatic ring, or a thick Ring, A ⁴ is a monovalent 5-membered ring or 6-membered ring aromatic ring, or their condensed ring, at least one hydrogen of the aromatic ring or their condensed ring in A ³ and A ⁴ may pass fluorine, chlorine, cyanide Base, nitro, trifluoromethyl, trifluoromethoxy, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkyl ester with 1 to 5 carbons, 1 to 5 carbons Substituted by alkanoyl or thioalkyl having 1 to 5 carbon atoms, p is an integer of 0 or 1; R ¹ and R ² are each independently hydrogen, fluorine, chlorine, trifluoromethyl, or trifluoromethoxy A cyano 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) Group; -Y ¹ -Y ² -PG (2) In formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-; Y ² is a single bond or has 1 to 20 carbon alkylene groups, at least one of the alkylene groups -CH ₂ -may be substituted by -O-, -COO-, -OCO-, -CH = CH-, or -C≡C-; PG is a polymerizable group represented by any one of formulas (PG-1) to (PG-8); In the formulae (PG-1) to (PG-8), R ^{4 is} independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl. The liquid crystal compound according to item 1 of the scope of the patent application, wherein at least one of R ¹ and R ² in the formula (1) is a group represented by the formula (2). The liquid crystal compound according to item 1 of the scope of the patent application, wherein in the formula (1), A ¹ and A ² are each independently 1,4-phenylene or 1,4-cyclohexyl. In these groups, At least one hydrogen can be passed through fluorine, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons, or alkane having 1 to 5 carbons Z ¹ and Z ² are each 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 item 1 of the scope of patent application, wherein in the formula (1), at least one of A ¹ and A ² is 1,4-cyclohexyl. The liquid crystal compound according to item 1 of the scope of patent application, wherein in 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 crystal compound according to item 1 of the scope of patent application, wherein in the formula (1), R ¹ and R ² are groups represented by the formula (2-1), In formula (2-1), Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-, and Y ² is a single bond or an alkylene group having 1 to 20 carbon atoms. 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 item 1 of the scope of patent application, wherein in formula (1), Q ¹ is a group represented by any one of formulas (4-1) to (4-9), In formulas (4-1) to (4-9), X ² is -O- or -S-, at least one of -CH = may be substituted by -N =, and at least one hydrogen may be substituted by fluorine, chlorine, and cyano. , Trifluoroacetamido, trifluoromethyl, alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkyl ester with 1 to 5 carbons, or alkyl with 1 to 5 carbons Superseded by; * indicates the bonding site. A liquid crystal composition containing at least one of the liquid crystal compounds according to the first patent application scope. A liquid crystal composition containing at least one liquid crystal compound according to item 1 of the scope of patent application, and at least one selected from the group of compounds represented by formula (M1) and formula (M2), In formula (M1) and formula (M2), A ^{M is} independently 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2,5-di Group, fluorenone-2,7-diyl or naphthalene-2,6-diyl, among these groups, at least one hydrogen may be passed through fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl, Substituted by difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkyl ester having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbons ; Z ^M is 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 with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons or 1 to 20 carbons Alkyl ester of 20; q is an integer of 1 to 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 -. A liquid crystal composition containing at least one liquid crystal compound as described in item 1 of the scope of patent application and at least one compound represented by formula (M1), In formula (M1), A ^{M is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one of A ^M is 1,4-cyclohexyl. Among these groups, at least one hydrogen may be Via fluorine, chlorine, trifluoroacetamido, difluoromethyl, trifluoromethyl, alkyl group with 1 to 5 carbon atoms, alkoxy group with 1 to 5 carbon atoms, alkyl ester with 1 to 5 carbon atoms, or Carbon atoms of 1 to 5 are 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, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, 1-20 alkane Group, alkenyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms or alkyl ester with 1 to 20 carbon atoms; a is an integer from 0 to 20; R ^M is hydrogen or methyl, and Y ^M is Single bond, -O-, -COO-, -OCO-, or -OCOO-. The liquid crystal composition according to any one of claims 8 to 10 of the scope of patent application, further comprising at least one chiral compound. The liquid crystal composition according to any one of claims 8 to 10 of the scope of patent application, further comprising at least one dichroic pigment compound. A polymer, which is a polymer obtained by irradiating ultraviolet light to the liquid crystal composition described in item 8 of the scope of patent application. An optically anisotropic film, which is a polymer according to item 13 of the scope of patent application, which has optical anisotropy. A polarizer includes the optically anisotropic film according to item 14 of the scope of patent application. A display element includes the optically anisotropic film according to item 14 of the scope of patent application. A display element includes the polarizer according to item 15 of the scope of patent application.