TWI677565B - Polymerizable liquid crystal composition, optically anisotropic film, polarizer, display element, and compound - Google Patents

Abstract

An object of the present invention is to provide a polymerizable liquid crystal composition capable of controlling wavelength dispersion characteristics and capable of producing an optically anisotropic film exhibiting low wavelength dispersion characteristics or reverse wavelength dispersion properties. According to the present invention, a polymerizable liquid crystal composition containing at least one compound represented by formula (1) can be used to produce a birefringence Δn (λ) with respect to light having a wavelength λ nm of Δn (450) / Δn (550) ≦ 1.05. An optically anisotropic film that exhibits low-wavelength dispersion characteristics or reverse wavelength dispersion properties.

Description

Polymerizable liquid crystal composition, optically anisotropic film, polarizer, display element, and compound

The present invention relates to a polymerizable liquid crystal composition that can be made into an optically anisotropic film with low wavelength dispersion characteristics or reverse wavelength dispersion, and also relates to a polymer obtained from the composition, an optically anisotropic film, and their use.

An optical compensation technology using a retardation plate for the purpose of wide viewing angle or high contrast of a liquid crystal display (LCD) is known. As such a retardation plate, a polymer film is generally used. Those who stretch to control birefringence are called stretch films.

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. The compound exhibits birefringence in a liquid crystal state, and its orientation is fixed by polymerization. The fixed alignment state of the polymer may include: homogeneous (horizontal alignment), tilt (tilt alignment), vertical (homeotropic) (vertical alignment), twist (twisted alignment), and the like. The retardation plate obtained by using a polymerizable liquid crystal compound exhibits a large birefringence compared with the stretch film used in the past, and therefore, it can be made into a thin film and can be directly applied to a substrate, so that an adhesive layer is not required. In addition, since a strong mesh can be constructed, it has excellent characteristics such as a small change rate of characteristics with respect to the external environment. Furthermore, since the three-dimensional refractive index can be easily controlled by the alignment control of the liquid crystal, it is also excellent in terms of moldability.

An optically anisotropic film having a 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 to be used for optical compensation in a liquid crystal mode of horizontal alignment such as an in-plane switching (IPS) mode, for example, the viewing of a polarizer Improvement of field angle 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. The ink is applied on an alignment-treated substrate, and the solvent is 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 solvent is removed and dried at room temperature until polymerization is performed. 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 have good compatibility with other liquid crystal compounds or high solubility in organic solvents. Furthermore, as the liquid crystal composition, it is necessary to maintain a long temperature near room temperature after the solvent is removed. Liquid crystal phase of time. 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.

In addition to this, the polymer obtained from the liquid crystal composition requires, in addition to the characteristics of optical anisotropy, high transparency, high mechanical strength, high adhesion to the substrate, low shrinkage, high heat resistance, and resistance to Advanced chemical properties.

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 to no, the refractive index change rate of ne to the wavelength is large, so the birefringence (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. However, a general optical anisotropic layer is used to design 1 / 2λ or 1 / When a 4λ plate or the like is used in parallel, the following problems arise due to the aforementioned wavelength dispersion: a change in the polarization state due to the wavelength occurs, and the light becomes colored. In order to prevent the above-mentioned problems, it is necessary to control the wavelength dispersion in order to be a phase difference designed at each wavelength. A material having low dependence of birefringence due to wavelength (low-wavelength dispersion characteristic) is required, or it changes with wavelength. A material with a large birefringence (inverse wavelength dispersion characteristic).

In recent years, in organic electroluminescence (EL) displays (Organic Light Emitting Display (OLED)), it has been known to use a 1/4 wavelength plate and Circular polarizer of a polarizer (Patent Document 4). In such applications, a shift in a phase difference due to a wavelength dispersion characteristic also changes a polarization state. Therefore, there is a problem that the anti-reflection function cannot be effectively obtained with respect to the total wavelength of the visible region, and a material having an inverse wavelength dispersion characteristic is required.

In order to obtain an optically anisotropic layer having inverse wavelength dispersion characteristics, a method of laminating two retardation layers at respective angles in the direction of the alignment axis has been proposed (Patent Document 5 and Patent Document 6). 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 a liquid crystal compound having reverse wavelength dispersion characteristics has been proposed (Patent Documents 7 to 11).

However, since the compound described in Patent Document 7 has a low birefringence, 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 the alignment uniformity due to the small aspect ratio, and further, due to the synthesis The path is long and difficult to manufacture. Since the compounds described in Patent Documents 8 and 9 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 Documents 10 and 11 have a high temperature range or a clear point of the liquid crystal phase, and require complicated steps such as polymerization by irradiating ultraviolet rays while heating. In addition, the compounds described in Patent Documents 7 to 11 have low solubility in organic solvents as a whole, and a liquid crystal phase retention time at room temperature is short. Therefore, the manufacturing margin is narrow and improvement is required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-372623 [Patent Document 2] International Publication No. 2005/38517 [Patent Document 3] US Patent Application Publication No. 2006/182900 [Patent Document 4] Japanese Patent Laid-Open Publication Japanese Patent Publication No. 8-321381 [Patent Document 5] Japanese Patent Publication No. 10-68816 [Patent Document 6] Japanese Patent Publication No. 2001-4837 [Patent Document 7] Japanese Patent Publication No. 2010-522893 [Patent Document 8] Japanese Patent Laid-Open No. 2009-179563 [Patent Literature 9] International Publication No. 2012/060011 [Patent Literature 10] Japanese Patent Laid-Open No. 2005-289980 [Patent Literature 11] Japanese Patent Laid-Open No. 2010-31223 Gazette [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]

An object of the present invention is to provide a polymerizable liquid crystal composition having a high transmittance in a visible region and a long retention time of a liquid crystal phase at room temperature, so it is easy to handle, and wavelength dispersion can be controlled without requiring complicated steps. Characteristics, and an optically anisotropic film exhibiting low-wavelength dispersion characteristics or reverse wavelength dispersion properties can be produced. [Technical means to solve the problem]

The inventors carried out active research repeatedly, and as a result, found that a polymerizable liquid crystal composition containing a specific compound having a substituent at the 2- or 3-position of 1,4-phenylene will solve the above-mentioned problems and complete the invention. That is, this invention is as follows.

[1] A polymerizable liquid crystal composition containing at least one compound represented by formula (1). [Chemical 1] (In the formula (1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one hydrogen in the 1,4-phenylene may be fluorine, chlorine, or triphenylene. Fluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbon atoms, among which A ¹ At least one of them is 1,4-cyclohexyl; Z ^{1 is} each independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- ; Z ² is a single bond, -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N- or -N = N-; G is (A) an aromatic ring containing at least one heteroatom and having π electrons of 6-20 A monovalent group, (B) a monovalent group containing at least one hetero atom and an aromatic ring connected to at least one aromatic ring, and having 6 to 20 π electrons, and (C) containing at least one A heterocyclic polycyclic aromatic ring and a monovalent group having 6 to 20 π electrons Or (D) a monovalent group having at least two or more π electrons including an aromatic ring, an aromatic ring containing at least one or more heteroatoms, and a polycyclic aromatic ring containing at least one or more heteroatoms At least one hydrogen in the group may be fluorine, chlorine, cyano, trifluoroacetamido, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or carbon number. 1 to 5 alkoxycarbonyl groups or 1 to 5 carbon alkyl groups are substituted; m is each independently an integer of 1 to 3; Y ^{1 is} each independently a single bond, -O-, -COO-,- OCO- or -OCOO-; Q ^{1 is} each independently a single bond or an alkylene group having 1 to 20 carbon atoms. At least one of the alkylene groups may be -CH ₂ -via -O-, -COO-, or- Substituted by OCO-; PG is independently a polymerizable group represented by any one of formula (PG-1) to (PG-9)) [Chem 2] (In formulas (PG-1) to (PG-9), R ^{1 is} independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl) [2] The polymerizable liquid crystal according to [1] A composition wherein, in Formula (1), Z ² is a single bond or -CH = CH-; G is a group represented by Formula (G-1) to Formula (G-9). [Chemical 3] (In the formulae (G-1) to (G-9), X ¹ is -O-, -S-, or -NR ^2- , and R ² is hydrogen, an alkyl group having 1 to 5 carbon atoms, and carbon number 1 ~ 5 alkylsulfonyl or phenyl which may have a substituent; at least one -CH = may be substituted by -N =, wherein, in formula (G-1) and formula (G-5), at least one -CH = For -N =, at least one hydrogen may be passed through fluorine, chlorine, cyano, trifluoroacetamido, trifluoromethyl, phenyl which may have a substituent, alkyl having 1 to 5 carbons, and carbon having 1 to 5 carbon atoms. Substituted with alkoxy, alkoxycarbonyl having 1 to 5 carbons or alkanoyl having 1 to 5 carbons) [3] The polymerizable liquid crystal composition according to [1] or [2], wherein: In Formula (1), PG is a polymerizable group represented by Formula (PG-1). [4] The polymerizable liquid crystal composition according to [2], wherein in the formula (1), G is represented by the formula (G-6), the formula (G-8), or the formula (G-9). [5] The polymerizable liquid crystal composition according to any one of [1] to [4], further containing at least one selected from the group of compounds represented by formula (M1) and formula (M2). [Chemical 4] (In formula (M1) and formula (M2), A ^{M is} independently selected from 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2, Any divalent group of 5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, in which at least one hydrogen may pass through fluorine, chlorine, cyano, hydroxyl , Methylamino, trifluoroacetamido, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 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-, -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 = C (CH ₃ )-, -C (CH ₃ ) = N- , -N = N- or -C≡C-; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, and 2 to 20 carbons Alkenyl, 1-20 alkoxy or 1-20 alkoxycarbonyl; q is an integer of 1 to 4; a is an integer of 0 to 20; R ^M is hydrogen or methyl; Y ^M single , -O -, - COO -, - OCO- , or -OCOO-) [6] [5] The polymerizable liquid crystal composition of claim, wherein in formula (M1) and formula (M2), A ^M is independently The ground is 1,4-phenylene or 1,4-cyclohexyl. In the 1,4-phenylene, at least one hydrogen can pass through fluorine, an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Alkoxy, alkoxycarbonyl having 1 to 5 carbons, or alkanoyl having 1 to 5 carbons, wherein at least one of A ^M is 1,4-cyclohexyl, and Z ^{M is} each independently Single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH _2- , -CH ₂ CH ₂ COO-, or -OCOCH ₂ CH _2- . [7] The polymerizable liquid crystal composition according to any one of [1] to [6], further comprising at least one chiral compound. [8] The polymerizable liquid crystal composition according to any one of [1] to [7], further containing at least one dichroic pigment compound. [9] An optically anisotropic film obtained by irradiating light to the polymerizable liquid crystal composition according to any one of [1] to [8]. [10] The optically anisotropic film according to [9], wherein the birefringence Δn (450) for light with a wavelength of 450 nm and the birefringence Δn (550) for light with a wavelength of 550 nm satisfy The relationship of Δn (450) / Δn (550) ≦ 1.05. [11] A polarizing plate having the optically anisotropic film according to [9] or [10]. [12] A display element having the optically anisotropic film according to [9] or [10]. [13] A display element having the polarizing plate according to [11]. [14] A compound represented by the formula (1-1). [Chemical 5] (In formula (1-1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one hydrogen in the 1,4-phenylene may be fluorine or chlorine. , Trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbons, wherein, At least one of A ¹ is 1,4-cyclohexyl; Z ^{1 is} each independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-,- OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or- COOCH ₂ CH _2- ; m is an integer of 1 to 3; n is 0 or 1; X ¹ is -O-, -S- or -NR ^2- , R ² is hydrogen, and carbon number 1 to 5 Alkyl, alkanoyl or phenyl having 1 to 5 carbons; W ¹ is hydrogen, fluorine, chlorine, phenyl which may have a substituent, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons Y ^{1 is} independently a single bond, -O-, -COO-, -OCO-, or -OCOO-; Q ^{1 is} independently a single bond or an alkylene group having 1 to 20 carbon atoms, the alkylene group Group, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; PG is independently (Polymerizable group represented by any one of formula (PG-1) to (PG-9)) [Chemical Formula 6] (In formulas (PG-1) to (PG-9), R ^{1 is} independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl) [Effects of the Invention]

According to the present invention, it is possible to control the wavelength dispersion characteristics and easily manufacture an optically anisotropic film that exhibits low wavelength dispersion characteristics or reverse wavelength dispersion properties.

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, a liquid crystal compound is a general term for a compound having a liquid crystal phase and a compound that does not have a liquid crystal phase but can be used 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 polymers by polymerizing monomers using methods such as light, heat, and catalysts. Among liquid crystal compounds, a liquid crystal compound having a polymerizable group is 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 a 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 simplification 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" in addition to including 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. It also includes 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, Q ¹ in the formula (2) is an alkylene group having 1 to 20 carbon atoms, and at least one -CH ₂ -in the alkylene group may be substituted with -O- or the like, but in the case, The number of carbons containing a substituted alkylene group using -O- or the like will not exceed 20. The same applies to other definitions.

In the case of the following description as a chemical formula, a straight line from A to B means a bond, and means that the hydrogen in A is substituted with a group B, and its position is arbitrary. X represents the number of substituted groups B. When X is 0, it means that B is absent and unsubstituted. [Chemical 7]

In addition, in the case of a description having a group as shown in the following C as a chemical formula, the wave line portion is referred to as a bonding position as a group. [Chemical 8]

<< Compound >> The polymerizable liquid crystal composition (hereinafter sometimes simply referred to as the "polymerizable liquid crystal composition of the present invention") as an embodiment of the present invention is characterized by containing at least one compound represented by formula (1). By using the polymerizable liquid crystal composition of the present invention, a birefringence Δn (450) with respect to light with a wavelength of 450 nm and a birefringence Δn (550) with respect to light with a wavelength of 550 nm can be produced to satisfy Δn (450) / An optically anisotropic film having a relationship of Δn (550) ≦ 1.05, that is, an optically anisotropic film exhibiting low-wavelength dispersion characteristics or reverse wavelength dispersion characteristics. 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 and the like is bonded to the core skeleton. On the other hand, the compound represented by formula (1) of the present invention has an aromatic ring at the 2- or 3-position of the 1,4-phenylene group directly, or has an aromatic ring through a double bond as the core skeleton. The mechanism of obtaining an optically anisotropic film exhibiting low-wavelength dispersion characteristics or reverse wavelength dispersion by containing a compound represented by formula (1) can be examined as follows. As shown by Lorentz-Lorenz's formula, the wavelength dispersion of the refractive index has a close relationship with the absorption waveform of a substance. In the region where the maximum light absorption of the substance occurs, there is an abnormal dispersion region where the refractive index sharply increases as the absorption wavelength approaches from the long wavelength side to the short wavelength side (with the wavelength becoming shorter). That is, by introducing a substituent that is rigid and elongates the conjugate system at the side, the absorption in the short-axis direction can be extended to the long wavelength region, and the refractive index change rate of no (normal refractive index) with respect to the wavelength can be accompanied by this Increase. In addition, by introducing a cyclohexane ring or the like in the long axis direction, the absorption in the long axis direction can be shortened, and the refractive index change rate of ne (abnormal refractive index) with respect to the wavelength can be reduced. It is considered that the two effects can control the wavelength dispersion characteristics of the birefringence. In addition, the polymerizable liquid crystal composition of the present invention can be formed to (1) show a good liquid crystal phase near room temperature; (2) show a good solubility to an organic solvent; (3) even after removing the solvent A composition that can maintain the characteristics of liquid crystals for a long period of time at room temperature. Furthermore, the obtained film is excellent in optical anisotropy, transparency, heat resistance, adhesion, dimensional stability, and mechanical strength. It can be said that the polymerizable liquid crystal composition of the present invention is a material very suitable for the production of an optically anisotropic film. Hereinafter, the compound represented by Formula (1) will be described in detail. In addition, in the polymerizable liquid crystal composition of the present invention, the compound represented by the formula (1) is not limited to one type, and may include two or more kinds of compounds equivalent to the formula (1).

[Chemical 9] In the formula (1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one is 1,4-cyclohexyl. Here, A ¹ in the presence of the above two cases, A ¹ may be the same or different. In order to have lower wavelength dispersion characteristics, 1,4-cyclohexyl is more preferable, and to have a larger birefringence, 1,4-phenylene is more preferable. In the 1,4-phenylene, at least one hydrogen may pass through fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or 1 to 5 carbons. It is substituted by an alkoxycarbonyl group or an alkyl fluorenyl group having 1 to 5 carbon atoms. However, in order to impart high liquid crystallinity to the compound, it is preferably unsubstituted.

In formula (1), Z ^{1 is} independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH ₂ -, -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, or -COOCH ₂ CH _2- . Here, in a case where there are two or more Z ^1, Z ¹ may be the same or different. When Z ¹ is -COO-, -OCO-, -CH ₂ CH ₂ COO-, or -OCOCH ₂ CH _2- , the compound has high liquid crystallinity and can be produced at low cost. In addition, when at least one of Z ¹ is -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- , it further has good miscibility with other liquid crystal compounds and organic solvents, and can reduce the transparency point. , Which can further reduce the recrystallization. In addition, in order for the compound represented by formula (1) to have high liquid crystallinity and good miscibility with other liquid crystal compounds and organic solvents, m is an integer of 1 to 3, respectively.

In formula (1), Z ² is a single bond, -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, or -N = N-. Considering the stability or reliability of the compounds, as well as simplicity, Z ² is preferably a single bond or manufactured -CH = CH-, Z ² is a single bond in the case where, tends to have excellent light resistance, in Z ² When it is -CH = CH-, it tends to be excellent in wavelength dispersion characteristics.

In the present specification, the heteroaromatic ring includes (A) an aromatic ring containing at least one or more heteroatoms, (B) an aromatic ring containing at least one or more heteroatoms and connected to at least one or more aromatic rings, and (C) containing A polycyclic aromatic ring having at least one heteroatom, and (D) at least two polyaromatic rings including an aromatic ring, an aromatic ring including at least one heteroatom, and a polycyclic aromatic ring including at least one heteroatom. Above the ring. The aromatic ring also includes fluorine, chlorine, cyano, trifluoroacetamido, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, and 1 to 6 carbons. Rings of substituents such as 5 alkoxycarbonyl groups or 1 to 5 carbon alkyl groups. G in Formula (1) is a heteroaromatic ring having 6 to 20 π electrons. The hetero atom means an atom other than carbon and hydrogen. In order to have high liquid crystallinity, good miscibility with other liquid crystalline compounds and organic solvents, and low wavelength dispersion characteristics, the groups represented by the formulae (G-1) to (G-9) are preferred. [Chemical 10] In the formulae (G-1) to (G-9), X ¹ is -O-, -S-, or -NR ^2- , and R ² is hydrogen, an alkyl group having 1 to 5 carbon atoms, and 1 to 6 carbon atoms. Alkyl group of 5 or phenyl which may have a substituent; at least one -CH = may be substituted by -N =, wherein, in formula (G-1) and (G-5), at least one -CH = is -N =, at least one hydrogen may be fluorine, chlorine, cyano, trifluoroacetamido, trifluoromethyl, phenyl which may have a substituent, alkyl group having 1 to 5 carbon atoms, It is substituted by an alkoxy group, an alkoxycarbonyl group having 1 to 5 carbon atoms, or an alkyl fluorenyl group having 1 to 5 carbon atoms. Examples of the "substituent" of "phenyl which may have a substituent" include fluorine, chlorine, cyano, trifluoroacetamido, trifluoromethyl, alkyl having 1 to 5 carbons, and carbon 1 An alkoxy group of 5 to 5, an alkoxycarbonyl group of 1 to 5 carbons, or an alkylfluorenyl group of 1 to 5 carbons. In order to have lower wavelength dispersion characteristics, a group represented by the formula (G-6), (G-8), or (G-9) is preferable, and in order to produce the compound with high liquid crystallinity and inexpensively, Preferred is a group represented by the formula (G-6).

In formula (1), Y ^{1 is} each independently a single bond, -O-, -COO-, -OCO-, or -OCOO-, and Q ^{1 is} each independently a single bond or an alkylene group having 1 to 20 carbon atoms. In the alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-. When Q ¹ is an alkylene group having 1 to 20 carbon atoms, it has high liquid crystallinity and good miscibility with other liquid crystal compounds and organic solvents.

PG is a polymerizable group represented by any one of formulas (PG-1) to (PG-9). [Chemical 11] In Formulas (PG-1) to (PG-9), R ^{1 is} each independently hydrogen, halogen, methyl, ethyl, or trifluoromethyl. With regard to the selection of the polymerizable group represented by the formulas (PG-1) to (PG-8), an appropriate polymerizable group can be selected according to the production conditions of the film. However, when a film is produced by a commonly used photopolymerization method, in terms of high hardenability, solubility in a solvent, ease of handling, and the like, it is preferable to express the selection formula (PG-1) Acryl or methacryl.

Among the compounds represented by the formula (1), low-wavelength dispersion characteristics, good liquid crystallinity, low transparency point, high solubility in organic solvents, high compatibility with other compounds, and In terms of easily and inexpensively producing a compound, a compound represented by formula (1-1) is preferred. [Chemical 12] In Formula (1-1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, and at least one hydrogen in the 1,4-phenylene may be fluorine, chlorine, Substituted by trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbons, among which A ¹ in at least one of 1,4-cyclohexylene, Z ¹ each independently a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 O -, - OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- , m are each independently an integer of 1 to 3, n is 0 or 1, X ¹ is -O-, -S-, or -NR ^2- , R ² is hydrogen, and alkane having 1 to 5 carbon atoms Carbon, alkanoyl or phenyl having 1 to 5 carbons, W ¹ is hydrogen, fluorine, chlorine, phenyl which may have a substituent, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-, and Q ¹ is a single bond or an alkylene group having 1 to 20 carbon atoms. at least one -CH ₂ - may be -O -, - COO- or -OCO- substituted, PG are each independently of formula (PG-1 ~ Of formula (PG-9) according to any one of the polymerizable group represented.

Preferable examples of the compound represented by the formula (1) are shown below. However, it is not limited to the preferable examples shown below.

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

Formula (1-1-1) to Formula (1-1-17), Formula (1-2-1) to Formula (1-2-5), Formula (1-3-1) to Formula (1-3 -8) or in formulae (1-4-1) to (1-4-9), R ² is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkyl fluorenyl group having 1 to 5 carbon atoms, or may have a substituent Phenyl, Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-, and Q ¹ is a single bond or an alkylene group having 1 to 20 carbon atoms. At least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, and PG is a polymerizable group represented by the formula (PG-1) to (PG-9).

The compound represented by formula (1) 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). For example, a compound represented by the formula (1-1) can be synthesized by a reaction step represented by the following formula. [Chemical 18] As for the 1,4-phenylene group of the core skeleton of the compound represented by the formula (1-1), for example, a benzenediol derivative having a reactive functional group such as 2,5-dimethoxybenzaldehyde can be used. To form. Here, in the formula, X is -O-, -S-, or -NH-. Specifically, an aldehyde of 2,5-dimethoxybenzaldehyde can be reacted with 2-methylbenzothiazole to introduce a benzothiazole structure via a double bond. In addition, the 2-aminothiophenol can be reacted to introduce a directly bonded benzothiazole structure. By deprotecting the structure and diesterifying the structure, a compound represented by the formula (1-1) can be derived. In addition, 1,4-cyclohexyl can be introduced by using 4-hydroxycyclohexanecarboxylic acid or the like as shown in the following formula. [Chemical 19] Here, in the formula, r is an integer of 2-12. The structure of the synthesized compound can be confirmed by, for example, a proton nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrum.

The alignment in the liquid crystal compound is classified into homogeneous, homeotropic, tilted, twisted, and the like based on the magnitude of the tilt angle and the like. The tilt angle is the alignment state of the liquid crystal compound and the angle between the support substrates. Parallel refers to a state where the alignment state is parallel to the substrate and aligned in one direction. Examples of the inclination angle in the parallel alignment are 0 to 5 degrees. Vertical refers to a state where the alignment state is perpendicular to the substrate. Examples of the inclination angle in the vertical alignment are 85 degrees to 90 degrees. Inclined refers to a state where the alignment state rises from parallel to vertical as it moves away from the substrate. Examples of the tilt angle (tilt angle) in the tilt alignment are 5 degrees to 85 degrees. Twisting refers to a state in which the alignment state is parallel to the substrate, but the spiral axis is twisted in a step shape at the center. Examples of the inclination angle in the torsional alignment are 0 to 5 degrees.

<< Liquid crystal composition >> The polymerizable liquid crystal composition of the present invention contains at least one compound selected from the group of compounds represented by formula (1). The polymerizable 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 polymerizable 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 to form a film, it becomes a parallel alignment or a hybrid alignment. In addition, when a non-polymerizable or polymerizable optically active compound described later is added to the polymerizable 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 polymerizable liquid crystal composition of the present invention, vertical alignment is easily obtained.

The polymerizable liquid crystal composition of the present invention contains 30% by weight or more, preferably 50% by weight or more of the present invention selected from the formula (1), based on 100% by weight of the total amount of the compound having a polymerizable group. At least one of the group of compounds. When the content of the compound (1) is within the above range, the wavelength dispersion of the birefringence can be easily controlled, and the effect of the polymer of the present invention can be significantly exhibited.

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

[Chemical 20] In the formula (LC), A ^{3 is} independently selected from 1,4-phenylene, 1,4-cyclohexyl, pyridine-2,5-diyl, and 1,3-dioxane-2,5. -Diyl and any divalent radical of naphthalene-2,6-diyl, in which at least one hydrogen can pass through fluorine, chlorine, cyano, hydroxyl, formamyl, trifluoroacetamyl , Difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 1 to 5 carbons or alkyl fluorenyl having 1 to 5 carbons Substituted; Z ^{3 is} each independently a single bond or an alkylene group having 1 to 20 carbon atoms. Among the alkylene groups, at least one -CH ₂ -may pass through -O-, -CO-, -COO-,- OCO-, -CH = CH-, -CF = CF- or -C≡C-, at least one hydrogen may be replaced by halogen; b is an integer of 1 to 5; R ^{3 is} independently hydrogen, fluorine, Chlorine, cyano, hydroxy, formamyl, trifluoroethyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, said alkyl At least one of -CH ₂ -may be replaced by -CH = CH-.

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

[Chemical 21]

[Chemical 22]

[Chemical 23]

The other polymerizable liquid crystal compound is preferably a compound represented by the following formula (M1), formula (M2), and formula (M3).

[Chemical 24] In formula (M1), formula (M2), and formula (M3), A ^{M is} independently selected from 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, Any of dipyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl. In the divalent group, at least one hydrogen may pass through fluorine, chlorine, cyano, hydroxy, formamyl, trifluoroacetamido, difluoromethyl, trifluoromethyl, alkyl group having 1 to 5 carbons, and carbon. 1 to 5 alkoxy groups, 1 to 5 carbon alkoxycarbonyl groups or 1 to 5 carbon alkyl groups; Z ^M is a single bond, -OCH _2- , -CH ₂ O each independently -, -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- , -COOCH ₂ CH _2- , -CH = CH-, -N = CH- , -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- or -C≡C-; X ^M is hydrogen, fluorine, chlorine, trifluoro Methyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons or alkoxycarbonyl having 1 to 20 carbons ; Q is an integer from 1 to 4; c and d is an integer of 0 to 3, and has a relationship of 1 ≦ c + d ≦ 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-; Q ^M is a single bond, -O-, or -COO-. Here, when q, c, or d is 2 or more, the A ^M and Z ^M may be different in each iteration.

Moreover, among the compounds represented by said formula (M1), a formula (M2), and a formula (M3), it is more preferable to use the compound represented by a formula (M1) or a formula (M2).

In terms of exhibiting low-wavelength dispersion characteristics, good liquid crystallinity, low transparent point, high solubility in organic solvents, high compatibility with other compounds, easy and inexpensive production of compounds, etc., In the formula (M1) or (M2), a compound represented by the following is more preferable: A ^M is 1,4-phenylene or 1,4-cyclohexyl, and at least one is 1,4- Cyclohexyl, Z ^M is a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH _2- , -CH ₂ CH ₂ COO-, or -OCOCH ₂ CH _2- .

The compound represented by 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. In addition, by increasing the amount of addition, it becomes easy to obtain vertical alignment. The compound represented by formula (M2) is a difunctional polymerizable liquid crystal compound, and the polymer has a three-dimensional structure, and thus is a harder polymer than the compound represented by 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 25]

[Chemical 26] In the formulae (M1-1) to (M1-24), 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 27]

[Chemical 28]

[Chemical 29] 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.

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

[Chemical 30]

[Chemical 31] In the formulae (M3-1) to (M3-10), R ^{M is} each independently hydrogen or methyl, and a is each 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.

The total amount of at least one compound selected from the compound group of the present invention represented by the formula (1) and at least one compound selected from the compound group represented by the formula (M) is 100% by weight. The polymerizable liquid crystal composition preferably contains 50% to 95% by weight of at least one selected from the group of compounds of the present invention represented by formula (1). When the content of each component in the liquid crystal composition is within the above range, a liquid crystal having a wide liquid crystal phase near room temperature, a wavelength dispersion in which birefringence can be easily controlled, and a good coatability can be obtained.组合 物。 Composition.

The polymerizable liquid crystal composition of the present invention may further include a surfactant. The surfactant is preferably a nonionic surfactant, and 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 or suppressing air. Effects of tilt alignment on the interface side.

Based on the total weight of the group of compounds represented by the formula (1) (wherein, when it contains other liquid crystal compounds or other polymerizable liquid crystal compounds, it is the group of compounds represented by the formula (1) The total weight is preferably 0.0001 to 0.5 in a weight ratio 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. Examples of the silicone-based nonionic surfactants include Polyflow ATF-2 manufactured by Kyoeisha Chemical Co., Ltd., which contains unmodified silicone or modified silicone as a main component, and Granoller. (Glanol) 100, Granol (115), Granol (400), Granol (410), Granol (435), Granol (440), Granol (450), Glanol) B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK- 333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK-3510, and BYK-3570.

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

Examples of the hydrocarbon-based nonionic surfactant include Polyflow No. 3, Polyflow No. 50EHF, and Polyflow containing acrylic polymer as a main component. No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, Poly Poly Flow No. 95, Poly Flow 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 order to achieve integration with the polymerizable liquid crystal compound, the surfactant may have a polymerizable group. Examples of the polymerizable group introduced into the surfactant include an ultraviolet (Ultra Violet, UV) reactive functional group, a thermally polymerizable functional group, and the like. From the viewpoint of reactivity with a polymerizable liquid crystal compound, a UV-reactive functional group is preferred.

In order to optimize the applicability to a substrate, a surfactant classified as a (substrate) wetting agent may be used in combination. The wetting agent has the effect of reducing the surface tension of the polymerizable liquid crystal composition and improving the spreadability to the coating substrate. Examples of such wetting agents: Polyflow series (KL-100, KL-700, LE-604, LE-605, LE-606), TEGO Twin series (4000 ), TEGO Wet (KL245, KL250, KL260, KL265, KL270, KL280, KL500, KL505, KL510), etc. In addition, as an adjuvant for a wetting agent, a surfactant containing a fluorinated modified polymer or a fluorine-modified acrylic polymer as a main component can also be applied. Examples of such surfactants include the 3000 series (for example, 3277, 3700, 3770, etc.) manufactured by AFCONA.

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. Based on the total weight of the group of compounds represented by the formula (1) (wherein, when it contains other liquid crystal compounds or other polymerizable liquid crystal compounds, it is the group of compounds represented by the formula (1) In terms of weight ratio, it 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 acid (eg acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), (meth) acrylic acid 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, methyl carvyl, ethyl carvyl, and butyl carvyl), N-vinylacetamidamine, p-tert-butylbenzoate, N, N- Dimethylaminobenzoate, vinylbenzoate, vinylvalerate, vinyl-2,2-dimethylbutanoate, vinyl-2,2-dimethylvalerate, 2-methyl- Ethylene 2-butyrate , Vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutyrate, dicyclopentyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate Ester, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentyl (meth) acrylate, dimethacrylate Cyclopentene ester, 2-propenyloxyethyl succinic acid, 2-propenyloxyethyl hexahydrophthalic acid, 2-propenyloxyethyl phthalic acid, 2-propenyloxy Ethyl-2-hydroxyethyl phthalic acid, 2-acrylic acid ethyl phosphate 2-acrylic acid, 2-methacrylic acid ethyl phosphate 2-acrylic acid, polymer with a degree of polymerization of 1 to 100 Mono (meth) acrylates or di (meth) acrylates of polyalkylene glycols such as ethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide, or alkane having 1 to 6 carbon atoms Mono- (meth) acrylates such as polyethylene glycol, polypropylene glycol, and polyalkylene glycols, such as copolymers of ethylene oxide and propylene oxide, having a degree of polymerization of 1 to 100 based on radicals.

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 hardening degree of the polymer. Examples of the polymerizable fluorene derivative having a cardo structure are shown in formulas (α-1) to (α-6).

[Chemical 32] 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 33] 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 rate, 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) 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, Irgacure 369, Ignacure (Irgacure) 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure ) 1850, Irgacure 1870, Darocure 4265, Darocure MBF, Darocure TPO, Irgacure 784, Irgacure 754, Yanjia Irgacure OXE01, Irgacure OXE02, Adeka Optomer N-1919, Adeka cruise NCI-831 Adeka Cruz (Adeka cruise) NCI-930 and so on. The said Darocure and Irgacure are the names of the products sold by BASF (Japan), Adeka Optomer and Ideco Cruz ( Adeka cruise) are the names of the products sold by Adeka (stock).

Examples of the photo-radical polymerization initiator include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine and 2- (p-butoxystyryl) -5-trichloro Methyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, benzophenone / michelone 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 Wait.

Based on the total weight of the group of compounds represented by the formula (1) (wherein, when it contains other liquid crystal compounds or other polymerizable liquid crystal compounds, it is the group of compounds represented by the formula (1) In terms of weight ratio, the preferable addition amount of the photo-radical polymerization initiator is 0.0001 to 0.20. The more preferable range of the weight ratio is 0.001 to 0.15. A more 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 properties, etc. 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, which are monofunctional thiols, and trihydroxy, which is a polyfunctional thiol. Methylpropane tris (3-mercaptopropionate), pentaerythritol tetras (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1), Pentaerythritol tetrakis (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. A known polymerization inhibitor can be used, and preferred examples thereof are 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methylene blue, and diphenyl. Diphenyl picryl hydrazide (DPPH), phenothiazine, N, N-dimethyl-4-nitrosoaniline and other nitroso compounds, o-hydroxybenzophenone, and 2H-1,3 -Benzothiazine derivatives such as 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-dimethylbutylene) -3- (trialkoxysilyl) -1-propaneamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxy Silane, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane, and the like. Also, 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 polymerizable 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 the solvent. Cloth the 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.

Phenamine solvents are 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, tert-butanol, sec-butanol, butanol, 2-ethylbutanol, N-hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-pentanol, hexafluoro-2-propanol, glycerol , 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 methyl ring Hexanol and so on.

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.

The glycol monoalkyl ether-based solvent is 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.

Aromatic hydrocarbon solvents are: benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, cumene, n-propylbenzene, tert-butylbenzene, sec-butylbenzene, n-butyl Benzene and tetrahydronaphthalene. 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. The 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. In consideration of 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 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 preferred range of the ratio is 10% to 50% by weight, and the more preferred range is 10% to 40% by 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 coated on a support substrate and dried to form a coating film. The coating film is irradiated with light to polymerize the liquid crystal composition, and the composition in the coating film is fixed in a nematic 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, polyketone sulfide, polyetherimide, polyfluorene, 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 sheet-like or film-like.

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 preferably 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 (ethylene, α-olefins, etc.), norbornene-based monomers and cycloolefin-based monomers (cyclopentene, cyclooctene, 5,6-bis Hydrodicyclopentadiene, etc.) addition copolymers, and modified products of these, specifically, include: ZEONEX, ZEONOR (both trade names, Japan ZEON (manufactured), Arton (trade name, manufactured by JSR), TOPAS (trade name, manufactured by TICONA), Appel (APEL) (trade name, manufactured by Mitsui Chemicals Co., Ltd.), Escena (trade name, manufactured by Sekisui Chemical Industry Co., Ltd.), OPTOREZ (trade name, Hitachi Chemical Co., Ltd.) Manufacturing).

The film (plastic film) containing these plastics that can be used as a support substrate can 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 the hydrophilization treatment is not particularly limited, and a corona treatment or a plasma treatment is preferred, 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 primer layer may be formed. As long as such an undercoat layer is used to improve the adhesion between a liquid crystal film and a plastic film, there is no problem even if it is an inorganic material or 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, or alkali-etched glass, borosilicate glass, and vermiculite ( flint glass).

When forming a liquid crystal film of parallel alignment and mixed alignment on a supporting substrate such as a glass substrate, a plastic film, or the like before forming a coating film of the liquid crystal composition, physical or mechanical surface treatment is performed by rubbing or the like. 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 roller, etc., and is brought into contact with a supporting substrate or a polymer film. A method in which the roller moves while rotating; a method in which the support substrate is moved while the roller is fixed. The rubbing treatment may be performed directly on the supporting substrate, or a polymer coating film such as polyimide, generally referred to as an alignment film, may be provided in advance on the supporting substrate, and the polymer coating film may be subjected to rubbing treatment. 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 its solution 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 surface treatment of the substrate by rubbing or the like.

When the solution of the polymerizable 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 heat-treating the coating film, the wavelength of light used in light irradiation, the amount of light irradiated by the light source, and the like depend on the type and composition ratio of the compound used in the liquid crystal composition, and the addition of a photopolymerization initiator. Presence or absence, addition amount, and the like are preferably in different ranges. 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 may be carried out above the liquid crystal phase transition point of the liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated 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. The method is a method of substantially completing the nematic alignment in the coating film by heating the coating film to a high temperature region of the temperature range, and then further reducing the temperature 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 the 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. The preferable range of the time is 10 seconds to 40 minutes, and the more preferable 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, it is preferable to set the heat treatment time to 5 seconds or more. In order not to reduce productivity, it is preferable to set the heat treatment time 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. A preferred range is 250 nm to 450 nm, and a more preferred range is 300 nm to 400 nm. Examples of light sources are: low-pressure mercury lamps (germicidal 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 . The preferable range of the light amount is 10 mJ / cm ² to 3000 mJ / cm ² , and the 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 amount of the surfactant added as one of the other components, and the like. The tilt angle of the liquid crystal film may be controlled 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 inclination angle of the parallel alignment is similar to 0 degrees from the substrate interface to the free interface, and is especially distributed between 0 degrees and 5 degrees. The alignment state is obtained by applying the polymerizable 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 polymerizable 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 polymerizable liquid crystal composition of the present invention can be used as a liquid crystal as a constituent element of a liquid crystal display element, in addition to being used as a raw material of a polymer described below.

[Chem 34]

[Chemical 35] 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. By the polymerization of the liquid crystal composition, the spiral structure is fixed. 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 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 central wavelength (λ) and the wavelength amplitude can be adjusted appropriately by changing n or pitch. (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, the 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, a moderate 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, an optically active compound having a large torque (HTP: helical twisting power) can be used to increase the amount of the optically active compound. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. The negative C plate becomes a vertical alignment nematic (VAN) type, a vertical alignment cholesteric (VAC) type, and an optically compensated birefringence (OCB) suitable for a liquid crystal display element. ) 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. To increase the pitch, for example, it is possible to use an optically active compound with a small torque or to reduce the amount of the optically active compound.

Any optically active compound may be used as long as the optically active compound can cause a helical structure and is appropriately mixed with a liquid crystal composition that becomes a matrix. In addition, it may be either a polymerizable compound or a non-polymerizable compound, and an optimal compound may be added according to 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 preferred range is from 0.1 μm to 50 μm, and a further preferred range is from 0.5 μm to 20 μm. The liquid crystal film preferably has a haze value of 1.5% or less, and preferably a transmittance of 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. As for the transmittance, it is preferable to satisfy these conditions in the visible light region.

The higher the birefringence (value of optical anisotropy) of the liquid crystal film, the thinner the thickness. 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 (Supertwisted Birefringence Effect), etc. Furthermore, the liquid crystal film may 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 can also 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 absorption polarizing plate doped with iodine, it is also preferably used for reflective type such as wire grid polarizing plate Optical compensation of polarizers.

The liquid crystal film may contain additives such as a dichroic dye. The dichroic pigment is preferably one having a maximum absorption wavelength (λ _MAX ) in a range of 300 nm to 700 nm. Examples of such dichroic pigments include acridine pigments, oxazine pigments, cyanine pigments, naphthalene pigments, azo pigments, and anthraquinone pigments. Among these, azo pigments are preferred. Examples of the azo pigment include a monoazo pigment, a diazo pigment, a triazo pigment, a tetraazo pigment, and a stilbene azo pigment, and the diazo pigment and the triazo pigment are preferred. 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.

The optically anisotropic film of the present invention has a wavelength that satisfies the relationship of Δn (450) / Δn (550) ≦ 1.05 at a birefringence Δn (450) at a wavelength of 450 nm and a birefringence Δn (550) at a wavelength of 550 nm. Dispersibility. An optically anisotropic film that satisfies the wavelength dispersion characteristics can improve visibility such as a color spot or a viewing angle, as compared with a conventionally formed optically anisotropic film using a polymerizable liquid crystal. In particular, it is more preferable to have a wavelength dispersibility satisfying a relationship of 0.75 ≦ Δn (450) / Δn (550) ≦ 1.05. If the value of Δn (450) / Δn (550) is too small, when the optimal delay is set with respect to green, the blue delay is changed from the optimal value to an excessively small value, and therefore the viewing angle characteristic is deteriorated. Conversely, if the value of Δn (450) / Δn (550) is too large, when the optimal delay is set with respect to green, the blue delay is changed from the optimal value to an excessively large value, so the viewing angle characteristic Worse. Unlike the conventional optically anisotropic film, the refractive index of the optically anisotropic film that satisfies the relationship has a low wavelength dispersion, and further has an inverse wavelength dispersion (increasing the birefringence as the wavelength becomes larger). It is possible to provide a further optimized optically anisotropic film material. [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 JNC Co., Ltd.) After removing the solvent from the spin-coated coating film on a 80 ° C hot plate, the coating film was sintered 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 analysis device An OPIPRO polarization analysis device manufactured by Shintec Co., Ltd. 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 a birefringence (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 the birefringence (Δn)> The birefringence (Δn) = delay based on the retardation and film thickness when the incident angle of light obtained from a liquid crystal film with parallel alignment is 90 ° with respect to the film surface. (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 (Re _{450 nm} ) measured with 450 nm light / retardation (Re _{550 nm} ) measured with 550 nm light. 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 compound (1-1-1-1) shown below was synthesized as follows. [Chemical 36]

5.0 g of 2,5-dimethoxybenzaldehyde and 4.49 g of 2-methylbenzothiazole were added to 40 mL of dimethylsulfinium (DMSO), and the reaction was performed under a nitrogen atmosphere at room temperature. Stir. 53 g of a 17.6 M aqueous NaOH solution was slowly added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. 500 mL of water was added to separate the precipitate by filtration, the crystals were washed with water, and the obtained crystals were dried under reduced pressure, thereby obtaining 8.8 g of a compound (ex-1).

8.8 g of the compound (ex-1) was added to 175 mL of dichloromethane, and the mixture was stirred while cooling at -78 ° C under a nitrogen atmosphere. To this was added 16.2 g of boron tribromide (BBr ₃ ). After the dropwise addition, the mixture was stirred at -78 ° C for 1 hour, and then stirred at room temperature for 16 hours. The reaction solution was poured into ice water for quenching, and the precipitate was separated by filtration. The obtained crystals were added to ethyl acetate and water for extraction. The obtained organic layer was washed with saturated sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure and dried under reduced pressure, whereby 7.8 g of compound (ex-2) was obtained.

25.0 g of trans-4-hydroxycyclohexanecarboxylic acid and 26.3 g of triethylamine were added to 125 mL of N, N-dimethylformamide (DMF). Stir while cooling below 10 ° C. 14.7 g of chloromethyl methyl ether was slowly added dropwise thereto. 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)). Purified and dried under reduced pressure, thereby obtaining 25.2 g of a compound (ex-3).

25.2 g of compound (ex-3), 42.9 g of compound (ex-4), and 3.3 g of 4-dimethylaminopyridine (DMAP) were added to 430 mL of dichloromethane. Stir while cooling under a nitrogen atmosphere. 60 mL of a dichloromethane solution of 29.0 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 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 = 4/1)). 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 isopropyl alcohol (IPA) at 40 ° C. Heat and stir 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-5).

1.5 g of the compound (ex-2), 5.0 g of the compound (ex-5), and 0.3 g of DMAP were added to 50 mL of dichloromethane, and stirred while cooling in a nitrogen atmosphere. 5 mL of a solution of 2.4 g 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 = 8/1)). After purification and recrystallization in methanol, 3.6 g of a compound (1-1-1-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-1-1) are as follows. Phase transition temperature (℃): C 67 N 82 I ¹ H-NMR (CDCl ₃ ; δppm): 8.00 (d, 1H), 7.89 (d, 1H), 7.54-7.34 (m, 5H), 7.15-7.06 ( m, 6H), 6.82 (d, 4H), 6.40 (d, 2H), 6.18-6.10 (m, 2H), 5.81 (d, 2H), 4.85-4.74 (m, 2H), 4.19-4.14 (m, 4H), 3.94 (t, 4H), 2.94-2.88 (m, 4H), 2.73-2.53 (m, 6H), 2.32-2.04 (m, 8H), 1.86-1.67 (m, 12H), 1.56-1.41 ( m, 12H).

[Example 2] The compound (1-1-5-1) shown below was synthesized as follows. [Chemical 37]

22.5 g of the compound (ex-3), 25.8 g of 2-propenyloxyethyl succinate, and 2.9 g of DMAP were added to 260 mL of methylene chloride, and the mixture was stirred while cooling under a nitrogen atmosphere. 52 mL of a dichloromethane solution of 25.9 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 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 = 4/1)). Purified and dried under reduced pressure. The obtained residue and 1.8 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 75 mL of THF and 37 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 dried under reduced pressure, whereby 33.5 g of a compound (ex-6) was obtained.

3.8 g of the compound (ex-2), 10.0 g of the compound (ex-6), and 0.7 g of DMAP were added to 100 mL of methylene chloride, and the mixture was stirred while cooling under a nitrogen atmosphere. 13 mL of a 6.3 g 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 dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 3/1)). Purified and recrystallized in methanol, thereby obtaining 4.5 g of a compound (1-1-5-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-5-1) are as follows. Phase transition temperature (℃): C 70 I ¹ H-NMR (CDCl ₃ ; δppm): 8.01 (d, 1H), 7.89 (d, 1H), 7.52-7.46 (m, 2H), 7.45-7.33 (m, 3H), 7.13-7.07 (m, 2H), 6.48-6.43 (m, 2H), 6.19-6.11 (m, 2H), 5.90-5.86 (m, 2H), 4.88-4.77 (m, 2H), 4.42- 4.33 (m, 8H), 2.73-2.55 (m, 10H), 2.34-2.27 (m, 2H), 2.25-2.09 (m, 6H), 1.87-1.68 (m, 4H), 1.60-1.46 (m, 4H ).

[Example 3] The following compound (1-1-10-1) was synthesized as follows. [Chemical 38]

Add 5.0 g of 2,5-dihydroxybenzaldehyde, 4.5 g of 2-aminothiophenol, and 3.8 g of sodium bisulfite to 50 mL of dimethylacetamide (DMA). Stir at 100 ° C for 4 hours under a nitrogen atmosphere. After leaving to cool, 100 mL of water was added to separate the precipitate by filtration, and the crystals were washed with water. The obtained crystal was recrystallized in heptane / methanol, thereby obtaining 8.6 g of a compound (ex-7).

1.9 g of the compound (ex-7), 7.2 g of the compound (ex-5), and 0.4 g of DMAP were added to 70 mL of dichloromethane, and stirred while cooling in a nitrogen atmosphere. 7 mL of a 3.5 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 dioxide, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 12/1)). Purified and recrystallized in methanol, thereby obtaining 6.3 g of a compound (1-1-10-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-10-1) are as follows. Phase transition temperature (° C): C 59 N 82 I ¹ H-NMR (CDCl ₃ ; δppm): 8.06 (d, 1H), 8.00 (d, 1H), 7.94 (d, 1H), 7.51 (t, 1H) , 7.45 (t, 1H), 7.24-7.17 (m, 2H), 7.10 (d, 4H), 6.80 (d, 4H), 6.40 (d, 2H), 6.17-6.08 (m, 2H), 5.81 (d , 2H), 4.82-4.74 (m, 2H), 4.19-4.14 (m, 4H), 3.94 (t, 4H), 2.90 (t, 4H), 2.79-2.71 (m, 1H), 2.63-2.54 (m , 5H), 2.30-2.17 (m, 4H), 2.12-2.05 (m, 4H), 1.82-1.68 (m, 12H), 1.56-1.41 (m, 12H).

<Production of polymerizable liquid crystal composition> [Example 4] 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) shown below. -1), compound (M2-1-1) and compound (M1-24-1) to prepare a liquid crystal composition shown in Table 1. [Chemical 39] 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. As the polymerization initiator, Irgacure 907 (Irg-907), Irgacure 184 (Irg-184) (both manufactured by BASF, Japan) or Edko Cruise NCI-930 (manufactured by Adeka), as the surfactant, Ftergent FTX-218 (manufactured by Neos), and cyclohexanone as the solvent.

[表 1] Table 1

[Comparative Example 1] In the same manner as the method described in Example 4, the compound (M2-7-1), compound (M1-15-1), compound (M1-16-1), and the following were used The compound (C-1) and the compound (C-2) were used to prepare a liquid crystal composition shown in Table 2. [Chemical 40]

[表 2] Table 2

＜ Production of Optical Anisotropic Film ＞

[Example 5] The liquid crystal composition (S-1) produced in Example 4 was applied to a glass substrate with an alignment film having been subjected to a rubbing treatment by spin coating. The substrate was heated at 80 ° C. for 2 minutes, cooled at room temperature for 1 minute, and the polymerizable liquid crystal layer from which the solvent was removed was polymerized in the air by ultraviolet irradiation to obtain an optical orientation in which the alignment state of the liquid crystal was fixed. Heterosexual film (F-1). 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.

[Example 6] In the same manner as the method described in Example 5, an optically anisotropic film was obtained from the liquid crystal composition (S-2) to the liquid crystal composition (S-7) produced in Example 4. F-2) ~ Optically anisotropic film (F-7). 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 5, an optically anisotropic film was obtained from the liquid crystal composition (SC-1) to the liquid crystal composition (SC-4) produced in Comparative Example 1. CF-1) ~ Optically Anisotropic Film (CF-4). The obtained optically anisotropic films were confirmed with a polarization microscope observation and a polarization analysis device, and as a result, they were confirmed to have parallel alignment.

<Optical characteristics of the optically anisotropic film> A measured value of a wavelength of 450 nm (Re) with a retardation of 90 degrees with respect to the film surfaces of the optically anisotropic films produced in Examples 5, 6, and Comparative Example 2 (Re ₄₅₀ ), the measured value (Re ₅₅₀ ) of the wavelength 550 nm, the film thickness, Δn at the wavelength 550 nm, and the wavelength dispersion characteristic (Re ₄₅₀ / Re ₅₅₀ ) are shown in Table 3.

[表 3] Table 3

According to Table 3, compared to the optically anisotropic film (F-1) to the optically anisotropic film (F-7) and the optically anisotropic film (CF-1), the wavelength dispersion characteristics showed a low value of 1.05 or less. In addition, the optically anisotropic film (F-1) and the optically anisotropic film (F-5) are compared with the optically anisotropic film (CF-2) and the optically anisotropic film (CF-3). Shows low wavelength dispersion characteristics. It was also confirmed that the optically anisotropic film (F-4) and the optically anisotropic film (F-7) have considerably lower wavelength dispersion characteristics than the optically anisotropic film (CF-4). From these circumstances, it is understood that the polymerizable liquid crystal composition of the present invention is a composition that can exhibit lower wavelength dispersion characteristics, and that the use of the polymerizable liquid crystal composition of the present invention can control the optically anisotropic film. Wavelength dispersion characteristics. In addition, it was confirmed that the optically anisotropic film (F-4) exhibited a value of 1 or less in the wavelength dispersion characteristic and had an inverse wavelength dispersion characteristic.

<Solubility of Compound in Solvent> The compound (1-1-1-1) synthesized in Example 1, the compound (1-1-10-1) synthesized in Example 3, and Comparative Example 1 were used. The solubility of the compound (C-1) in an organic solvent is shown in Table 4. Here, in Table 4, the solubility with respect to various solvents when the total weight of the compound and the solvent was 100% by weight and the compound was 15% by weight and 30% by weight was evaporated at 40 ° C. for 30 minutes. A person who completely dissolves is ○ and a person who has insoluble matter is x. The solvents used were cyclohexanone (CHN), anisole, propylene glycol monomethyl ether acetate (PGMEA), and methyl isobutyl ketone (MIBK).

[表 4] Table 4

Compared with the compound (C-2), it was confirmed that the compound (1-1-1-1) and the compound (1-1-10-1) have many types of organic solvents that can be dissolved, and can dissolve a large amount. When using a film in a substrate, it is necessary to select a solvent that matches the substrate, and it is important to have high solubility in a variety of solvents. In addition, if it can be dissolved at a high concentration, a thick film can be formed, and a desired phase difference can be easily obtained.

[Industrial Applicability] The polymerizable liquid crystal compound of the present invention can easily obtain an optically anisotropic film having a low wavelength dispersion property or an inverse wavelength dispersion property. Therefore, the obtained optically anisotropic film pair has, for example, a retardation film, an optical compensation film, a reflection film, a selective reflection film, an anti-reflection film, a field angle compensation film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, and A display element including a film or an element including an optically anisotropic film such as an elliptically polarizing element is preferred.

no

no

Claims (12)

A polymerizable liquid crystal composition containing at least one compound represented by formula (1-1),

(In formula (1-1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, in the 1,4-phenylene, at least one hydrogen may be fluorine, chlorine , Trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, C 1-5 alkoxycarbonyl or C 1-5 alkoxy, wherein, At least one of A ¹ is 1,4-cyclohexyl; Z ^{1 is} independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-,- OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or- COOCH ₂ CH _2- ; m is independently an integer of 1 to 3; n is 0 or 1; X ¹ is -O-, -S- or -NR ^2- , R ² is hydrogen, carbon number 1 to 5 Alkyl group, C1-C5 alkoxy group or phenyl group; W ¹ is hydrogen, fluorine, chlorine, optionally substituted phenyl group, C1-C5 alkyl group or C1-C5 alkoxy group Group; Y ^{1 is} independently a single bond, -O-, -COO-, -OCO- or -OCOO-; Q ^{1 is} independently a single bond or an alkylene group having 1 to 20 carbon atoms, the alkylene group group, at least one -CH ₂ - may be -O -, - COO- or -OCO- substituted; the PG are each independently of formula (PG-1) ~ formula (PG-9) according to any one of the Polymerizable group illustrated)

(In formula (PG-1) to formula (PG-9), R ^{1 is} independently hydrogen, halogen, methyl, ethyl or trifluoromethyl). The polymerizable liquid crystal composition as described in item 1 of the patent application, wherein in formula (1-1), PG is a polymerizable group represented by formula (PG-1). The polymerizable liquid crystal composition according to item 1 or 2 of the patent application scope, which further contains 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 selected from 1,4-phenylene, 1,4-cyclohexyl, 1,4-cyclohexenyl, pyridine-2, Any divalent group in 5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, in which at least one hydrogen can be substituted by fluorine, chlorine, cyano, hydroxyl , Methyl acetyl, trifluoroethyl acetyl, difluoromethyl, trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, C 1-5 alkoxycarbonyl Or C1-C5 alkylidene; 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 = C (CH ₃ )-, -C (CH ₃ ) = N- , -N = N- or -C≡C-; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, and carbon having 2 to 20 carbons Alkenyl, C 1-20 alkoxy or C 1-20 alkoxycarbonyl; q is an integer from 1 to 4; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-, -OCO-, or -OCOO-). The polymerizable liquid crystal composition as described in item 3 of the patent application scope, wherein in formula (M1) and formula (M2), A ^{M is} independently 1,4-phenylene or 1,4-cyclohexyl, In the 1,4-phenylene group, at least one hydrogen can be substituted by fluorine, C 1-5 alkyl group, C 1-5 alkoxy group, C 1-5 alkoxycarbonyl group or carbon number Substituted by 1-5 alkylene groups, wherein at least one of A ^M is 1,4-cyclohexyl, 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- . The polymerizable liquid crystal composition as described in item 1 or 2 of the scope of patent application further contains at least one chiral compound. The polymerizable liquid crystal composition according to item 1 or 2 of the scope of patent application further contains at least one dichroic dye compound. An optically anisotropic film obtained by irradiating light to the polymerizable liquid crystal composition according to any one of claims 1 to 6 of the patent application. An optically anisotropic film as described in item 7 of the patent application range, in which the birefringence Δn (450) with respect to light of wavelength 450nm and the birefringence Δn (550) with respect to light of wavelength 550nm satisfy △ The relationship of n (450) / △ n (550) ≦ 1.05. A polarizing plate having an optically anisotropic film as described in item 7 or 8 of the patent application. A display element having an optically anisotropic film as described in item 7 or 8 of the patent application. A display element having a polarizing plate as described in item 9 of the patent application scope. A compound represented by formula (1-1),

(In formula (1-1), A ^{1 is} independently 1,4-phenylene or 1,4-cyclohexyl, in the 1,4-phenylene, at least one hydrogen may be fluorine, chlorine , Trifluoromethyl, C 1-5 alkyl, C 1-5 alkoxy, C 1-5 alkoxycarbonyl or C 1-5 alkoxy, wherein, At least one of A ¹ is 1,4-cyclohexyl; Z ^{1 is} independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-,- OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or- COOCH ₂ CH _2- ; m is independently an integer of 1 to 3; n is 0 or 1; X ¹ is -O-, -S- or -NR ^2- , R ² is hydrogen, carbon number 1 to 5 Alkyl group, C1-C5 alkoxy group or phenyl group; W ¹ is hydrogen, fluorine, chlorine, optionally substituted phenyl group, C1-C5 alkyl group or C1-C5 alkoxy group Group; Y ^{1 is} independently a single bond, -O-, -COO-, -OCO- or -OCOO-; Q ^{1 is} independently a single bond or an alkylene group having 1 to 20 carbon atoms, the alkylene group group, at least one -CH ₂ - may be -O -, - COO- or -OCO- substituted; the PG are each independently of formula (PG-1) ~ formula (PG-9) according to any one of the Polymerizable group illustrated)

(In formula (PG-1) to formula (PG-9), R1 is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl).