KR20160025475A - Liquid crystal compound, liquid crystal composition and polymer thereof - Google Patents

Abstract

상기 식(1) 중에서, A¹ 및 A²는 각각 독립적으로 1,4-페닐렌 또는 1,4-시클로헥실렌이며; Z¹ 및 Z²는 각각 독립적으로 단결합, -OCH₂-, -CH₂O-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH₂CH₂COO-, -OCOCH₂CH₂-, -CH₂CH₂OCO- 또는 -COOCH₂CH₂-이며; m 및 n은 각각 0∼3의 정수이며; X¹은 -S-이며; Q¹은 방향환이며; R¹ 및 R²는 알킬이나 중합성 기를 가지는 기 등이다.Disclosure of the Invention An object of the present invention is to provide a liquid crystal composition having a low wavelength dispersion property capable of controlling refractive index anisotropy due to a wavelength and a compound exhibiting reverse wavelength dispersion property, and a liquid crystal composition containing the compound and having good applicability.
The present invention provides a compound represented by the following formula (1) and a liquid crystal composition comprising the compound.

In the formula (1), A ¹ and A ² are each independently 1,4-phenylene or 1,4-cyclohexylene; Z ¹ and Z ² are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH═CHCOO-, -OCOCH═CH-, -CH ₂ CH ₂ COO- _{, -OCOCH 2 CH 2 -, -CH} 2 CH 2 OCO- or -COOCH ₂ CH ₂ -, and; m and n are each an integer of 0 to 3; X ¹ is -S-; Q ¹ is an aromatic ring; R ¹ and R ² are alkyl or a group having a polymerizable group.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal compound, a liquid crystal composition, and a polymer thereof. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

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

In recent years, a liquid crystal compound having a polymerizable group has been utilized for an optically anisotropic film exhibiting birefringence (optical anisotropy) such as a reflection type polarizing plate and a retardation plate. This compound exhibits birefringence in a liquid crystal state, and its orientation is fixed by polymerization. Examples of the fixed orientation state of the polymer include homogeneous (horizontal orientation), tilt (oblique orientation), homeotropic (vertical orientation), and twist (torsional orientation).

An optically anisotropic film having a homogeneous orientation can be used as a composite retardation plate or a circular polarizer plate by combining with, for example, a half-wave plate, a quarter-wave plate, or a film having another optical function 1).

No. optically anisotropic film having a homeotropic orientation, and the orientation of the optical axis, n _z direction, since the refractive index in the optical axis direction is larger than the refractive index in a direction perpendicular to that, the refractive index ellipsoid, it is classified as positive C- plate. This positive C-plate can be applied to optical compensation such as a so-called IPS (In-Plane Switching) mode in which the liquid crystal mode is horizontally aligned, for example, by improving the viewing angle characteristic of a polarizing plate by combining with a film having another optical function (Non-Patent Documents 1 to 3, Patent Documents 2 and 3).

The optical properties required for the optically anisotropic film vary depending on the purpose and purpose, and various liquid crystal compounds have been developed as the compounds to be used. In addition, since it is often difficult to control the above-described anisotropy alone, it is used as a liquid crystal composition in combination with various compounds.

Such a liquid crystal composition is used as an ink by dissolving it in an organic solvent for the purpose of controlling the coating property. In order to produce a film having optical anisotropy using a liquid crystal composition, an ink is prepared by dissolving a liquid crystal compound, a photopolymerization initiator, a surfactant, and the like in an organic solvent to adjust solution viscosity, leveling property, and the like. This ink is applied to a substrate subjected to alignment treatment, and the solvent is dried to align the liquid crystal composition on the substrate. Next, ultraviolet rays are irradiated and polymerized to fix the alignment state. Normally, the organic solvent is dried and removed, and the polymerization is carried out at room temperature until polymerization. During this time, crystals and the like must not be precipitated and a uniform liquid crystal state must be maintained. Therefore, the polymerizable compound used in the liquid crystal composition must maintain good compatibility with other liquid crystalline compounds, high solubility in an organic solvent, and furthermore, maintain liquidity for a long time at around room temperature. Further, the organic solvent is required to have high solubility in an organic solvent having high stability in consideration of the influence on the environment or human body.

In addition to the properties of optical anisotropy, the polymer obtained from the liquid crystal composition is also required to have high transparency, strong mechanical strength, high adhesion to substrates, low shrinkability, high heat resistance, and high chemical resistance.

In an optically anisotropic layer formed by rod-shaped molecules, usually, two refractive indices ne (anomalous refractive index in a direction parallel to the molecular long axis) and no (refractive index in a direction perpendicular to the molecular long axis) of an anisotropic molecule ) Becomes smaller as the wavelength becomes larger. In this case, the refractive index anisotropy (? N = ne-no) becomes smaller as the applied wavelength increases, since the refractive index change ratio with respect to the wavelength is greater than no. On the other hand, in the case of a display device such as a liquid crystal display (LCD), the light source is white light composed of light having a wavelength of about 380 to 800 nm, but a 1/2 λ or 1/4 λ plate is designed and applied using a normal optical anisotropic layer , There arises a problem that the wavelength dispersion causes the change of the polarization state due to the wavelength and causes the light to become colored. In order to prevent this problem, it is necessary to control the wavelength dispersion so as to have a designed retardation at each wavelength, and it is necessary to use a material having a low dependence of the refractive index anisotropy due to the wavelength (low wavelength dispersion property) (Reverse wavelength dispersion characteristic) in which the refractive index anisotropy is increased.

In order to obtain an optically anisotropic layer having an inverse wavelength dispersion characteristic, a method has been proposed in which two retardation layers are formed by forming an angle in the direction of refractive index anisotropy, respectively (Patent Documents 4 and 5). However, such a laminate requires two retardation layers, and it is necessary to adjust the anisotropy angles of the two retardation layers, and the manufacturing complexity for forming a laminate, and the film thickness of the optically anisotropic layer And the problem of thickening.

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

However, since the compound described in Patent Document 6 has a low refractive index anisotropy, it is necessary to increase the film thickness in order to obtain a desired retardation. Moreover, since the aspect ratio is small, it is difficult to control the orientation uniformity and the synthesis route is long, There is a concern that the production is difficult. Since the compounds described in Patent Documents 7 and 8 have absorption in the visible region, the transmittance is likely to be low and color irregularity is likely to occur, and the compound is not suitable for use in optical applications. The compounds described in Patent Documents 9 and 10 have relatively good optical properties and a good production process, but they are further required to have improved properties in terms of mechanical strength, adhesiveness to a substrate, and heat resistance.

Japanese Patent Application Laid-Open No. 2002-372623 WO 05/38517 A1 U.S. Patent Application Publication No. 2006/182900 Japanese Patent Application Laid-Open No. 10-068816 Japanese Patent Application Laid-Open No. 2001-004837 Japan Specification No. 2010-522893 Japanese Patent Application Laid-Open No. 2009-179563 International Publication No. 2012/169424 A1 Japanese Patent Application Laid-Open No. 2005-289980 Japanese Patent Application Laid-Open No. 2010-031223

M. S. Park et al., IDW '04 FMC8-4 M. Nakata et al, SID '06 P-58 K. J. Kim et al, SID '06 Digest p.1158-1161

The present invention relates to a compound which exhibits a low wavelength dispersion property capable of controlling the refractive index anisotropy due to a wavelength and further exhibits an inverse wavelength dispersion property and has a good miscibility with other liquid crystalline compounds and organic solvents, A liquid crystal composition which exhibits a good liquid crystal phase (liquid crystal phase) at a relatively low temperature and exhibits good solubility in an organic solvent, and a liquid crystal composition which is excellent in mechanical strength and heat resistance by using the liquid crystal composition.

As a result of intensive studies, the present inventors have found that a compound having a benzothiophene, a benzofuran or an indole structure solves the above problems, and has completed the present invention. That is, the present invention is as follows.

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

[Chemical Formula 1]

(In the above formula (1)

A ¹ and A ² are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl or naphthalene- Wherein at least one hydrogen is selected from the group consisting of fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms , An alkyl ester having 1 to 5 carbon atoms, or an alkanoyl having 1 to 5 carbon atoms;

Z ¹ and Z ² are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO- _{, -CF 2 O-, -OCF 2 -} , -CH 2 CH 2 -, -CF 2 CF 2 -, -OCH 2 CH 2 O-, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH _{2 COO-, -OCOCH 2 CH 2 -} , -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 - _{, -CCH 3 = N-, -N =} N- , or -C≡C-, and;

m and n are each independently an integer of 0 to 3, and 1? m + n? 4;

X ¹ is -O-, -S- or -NR ³ -, and R ³ is hydrogen, alkyl of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;

Q ¹ is hydrogen, halogen or a monovalent organic group;

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

(2)

In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or alkylene having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -COO-, -OCO-, -CH = CH- or -C≡ C-; PG is a polymerizable group represented by any one of the following formulas (PG-1) to (PG-8). * Represents the binding site.

(3)

In the formulas (PG-1) to (PG-8), R ⁴ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl.

[2] The compound according to [1], wherein in the formula (1), Q ¹ is a group represented by the following formula (3) or (4).

[Chemical Formula 4]

(In the above formulas (3) and (4)

Z ³ are each independently a single bond, -COO- or -COS-;

Z ⁴ are each independently a single bond, -CH = CH-, -N = CH- , -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- or -C≡ C-;

R ⁵ is hydrogen, fluorine, chlorine, cyano or alkyl having 1 to 20 carbon atoms, and -CH ₂ - in the alkyl is -O-, -S-, -CO-, -COO-, -OCO-, OCOO-, in which hydrogen may be substituted with halogen;

A ³ is independently an aromatic ring of a divalent, a 5-membered or a 6-membered ring, or a condensed ring thereof, A ⁴ is an aromatic ring of a monovalent, 5-membered or 6-membered ring, or a condensed ring thereof, and A ³ And at least one hydrogen in the aromatic ring or the condensed ring thereof in A ⁴ is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms , An alkyl ester having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, or a thioalkyl having 1 to 5 carbon atoms;

and p is an integer of 0 to 2.)

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

[4] The compound according to any one of [1] to [3], wherein in the formula (1), X ¹ is -S-.

[5] In the formula (1), A ¹ and A ² each independently represents 1,4-phenylene or 1,4-cyclohexylene, wherein at least one hydrogen is fluorine, trifluoromethyl , Alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkylester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;

Z ¹ and Z ² are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH═CHCOO-, -OCOCH═CH-, -CH ₂ CH ₂ COO- _{, -OCOCH 2 CH 2 -, -CH} 2 CH 2 OCO- or -COOCH ₂ CH ₂ - which, [1] to [4] the compound according to any one of the.

[6] In the above formula (1), Q ¹ is a group represented by the formula (4), Z ⁴ in the formula (4) is a single bond, and p is an integer of 0 or 1. [5] The compound according to any one of [1] to [5].

[7] The compound according to any one of [1] to [6], wherein in the formula (1), at least one of A ¹ and A ² is 1,4-cyclohexylene.

[8] In the formula (1), at least one of Z ¹ and Z ² is -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ - 1] to [7].

In the above formula (1), R ¹ and R ² are groups represented by the above formula (2), PG is a polymerizable group represented by the above formula (PG-1) , And R < ⁴ > is hydrogen or methyl. [11] The compound according to any one of [1] to [8]

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

[Chemical Formula 5]

(In the formulas (4-1) to (4-9), X ² is -O- or -S-, at least one -CH = may be substituted with -N =, and at least one hydrogen is Which may be substituted with fluorine, chlorine, cyano, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms or alkanoyl of 1 to 5 carbon atoms * Represents the binding site)

[11] A liquid crystal composition comprising at least one compound according to any one of [1] to [10].

[12] A liquid crystal composition comprising at least one compound selected from the group consisting of [1] to [10] and at least one compound selected from the group of compounds represented by the following formulas (M1) and (M2)

[Chemical Formula 6]

(In the formulas (M1) and (M2)

A ^M is each independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, naphthalene-2,6-diyl, Diyl or fluorene-2,7-diyl, wherein at least one of the hydrogens is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoro Methyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;

Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF _{2 O-, -OCF 2 -, -CH} 2 CH 2 -, -CF 2 CF 2 -, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- , or -C≡C-, and;

X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester;

q is an integer of 1 to 4;

a is an integer from 0 to 20;

R ^M is hydrogen or methyl;

Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO-.)

[13] A liquid crystal composition comprising at least one of the compounds described in any one of [1] to [10] and at least one of compounds represented by the following formula (M1).

(7)

(In the above formula (M1)

A ^M is independently 1,4-phenylene or 1,4-cyclohexylene, but at least one of A ^M is 1,4-cyclohexylene, wherein at least one hydrogen is fluorine, chlorine, Trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;

Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ - ;

q is an integer of 1 or 2;

X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester;

a is an integer from 0 to 20;

R ^M is hydrogen or methyl;

Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO-.)

[14] A liquid crystal composition according to any one of [11] to [13], further comprising at least one chiral compound.

[15] A liquid crystal composition according to any one of [11] to [14], further comprising at least one dichroic dye compound.

[16] A polymer obtained by irradiating ultraviolet light to the liquid crystal composition according to any one of [11] to [15].

[17] An optically anisotropic film in which the polymer described in [16] has optical anisotropy.

[18] A polarizer having the optically anisotropic film according to [17].

[19] A display element having an optically anisotropic film according to [17].

[20] A display element having a polarizing plate according to [18].

The compound represented by the formula (1) of the present invention can be used alone or in combination with other known liquid crystal compounds or a composition containing several kinds thereof, and uniformly orienting the composition in an arbitrary form, thereby improving the refractive index anisotropy Thereby reducing the wavelength dependence or providing a material exhibiting the reverse wavelength dispersibility as shown above. The liquid crystal composition exhibits a good liquid crystal phase at a relatively low temperature and is excellent in properties such as good solubility in an organic solvent. The polymer obtained by polymerizing the liquid crystal composition of the present invention and the film containing the polymer are excellent in not only the effect on the wavelength dependency but also the excellent properties such as optical anisotropy, transparency, heat resistance, adhesion, dimensional stability and mechanical strength Do. Therefore, the polymer of the present invention is suitable for applications such as a retardation film, an optical compensation film, a polarizing element, a circularly polarizing element, an elliptically polarizing element, a color compensation film, and a viewing angle compensation film.

The usage of the terms in this specification is as follows. First, the meaning of the term " liquid crystalline property " is not limited to having a liquid crystal phase. That is, the liquid crystal compound is a generic term of a compound having a liquid crystal phase and a compound which does not have a liquid crystal phase but is useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase, etc. In most cases, it means a nematic phase. The liquid crystal lower limit temperature is a lower limit temperature indicating liquid crystal phase, and is a temperature transitioning from the liquid crystal phase to crystal. Polymerization means the ability of a monomer to polymerize and provide a polymer by means of light, heat, catalyst, or the like. A liquid crystal compound having a polymerizable group in a liquid crystal compound is referred to as a polymerizable liquid crystal compound, and a polymerizable liquid crystal compound is included in a liquid crystal compound. The polymerizable compound means a compound having a polymerizable group which does not exhibit liquid crystallinity. The case where the compound has one polymerizable group is sometimes referred to as a monofunctional or monofunctional compound. In the case where the compound has a plurality of polymerizable groups, the compound may be referred to as a polyfunctional or a name corresponding to the number of polymerizable groups. The compound represented by the formula (1) may be referred to as the compound (1). The compounds represented by other formulas may also be referred to by the same simplification method.

The term " at least one " used in describing the structure of a compound means at least one as to the number as well as the position. For example, the expression " at least one A may be substituted with B, C or D " means that at least one A is substituted by B, at least one A is substituted by C, Means not only a case where A is substituted by D but also a case where a plurality of A is substituted with at least two of B to D. However, the definition that at least one -CH ₂ - may be substituted with -O- does not include the substitution resulting from the linking group -OO-. When at least one -CH ₂ - is substituted with -O-, the number of carbon atoms does not exceed the stated range.

For example, Y ² in the formula (2) is alkylene having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkylene may be substituted with -O- or the like, The number of carbon atoms of the alkylene, including the substitution of R < 1 >, does not exceed 20 in this case. This rule also applies to other definitions.

«Compound»

For the purpose of wavelength dispersion control of refractive index anisotropy, which is an effect of the present invention, a compound represented by the general formula (1) is used. At this time, one kind may be selected from the compounds represented by the general formula (1), but two or more kinds may be selected and used.

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

[Chemical Formula 8]

In the formula (1), A ¹ and A ² each independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl or naphthalene Diyl. Here, when n and m are two or more, these A ¹ and A ² may be different for each repeating unit. In order to impart a high liquid crystallinity to a compound and to have good miscibility with other liquid crystalline compounds and organic solvents, A ¹ or A ² is independently 1,4-phenylene or 1,4-cyclohexylene It is more preferable that at least one of A ¹ and A ² is 1,4-cyclohexylene in order to decrease or reverse the wavelength dispersibility of the refractive index anisotropy. In the above 1,4-phenylene and 1,4-cyclohexylene, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoro Methyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms. However, in order to impart a high liquid crystallinity to the compound and to produce the compound at low cost, the substituent of the hydrogen is preferably fluorine, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, More preferably an alkyl ester of 1 to 5 carbon atoms or an alkanoyl of 1 to 5 carbon atoms.

In the formula (1), Z ¹ or Z ² each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, _{CONH-, -NHCO-, -CF 2 O-,} -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 -, -OCH 2 CH 2 O-, -CH = CHCOO-, -OCOCH = CH _{-, -CH 2 CH 2 COO-,} -OCOCH 2 CH 2 -, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH ₃ -, a -CCH ₃ = N-, -N = N-, or -C≡C-. Here, when n and m are two or more, these Z ¹ and Z ² may be different for each repeating unit. In order to impart a high liquid crystallinity to a compound, to have good compatibility with other liquid crystalline compounds and organic solvents, and to produce a compound at low cost, Z ¹ and Z ² each independently represents a single bond, -OCH ₂ -, -CH _{2 O-, -COO-, -OCO-, -CH} = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -CH 2 CH 2 OCO- or -COOCH ₂ CH ₂ -. In consideration of low transparency and good compatibility with other liquid crystalline compounds and organic solvents, at least one of Z ¹ and Z ² is preferably -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -.

In order to improve the liquid crystallinity of the compound of formula (1) and to have good miscibility with other liquid crystalline compounds and organic solvents, m and n are each an integer of 0 to 3, and 1? M + n? 4 desirable.

In the formula (1), X ¹ is -O-, -S- or -NR ³ -, and R ³ is hydrogen, alkyl of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms. It is preferable that X ¹ is -S- in order to have good compatibility with other liquid crystalline compounds and organic solvents and to lower or reverse the wavelength dispersibility of refractive index anisotropy.

Wherein R ¹ and R ² are each independently selected from the group consisting of hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, An alkyl ester having 1 to 20 carbon atoms, or a group represented by the following formula (2).

[Chemical Formula 9]

In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or alkylene having 1 to 20 carbon atoms, and any of -CH ₂ - in the alkylene may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C -; < / RTI > PG is a polymerizable group represented by any one of the following formulas (PG-1) to (PG-8). * Represents the binding site.

[Chemical formula 10]

In the formulas (PG-1) to (PG-8), R ⁴ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl.

Groups represented by the R ¹ or R ^2, the case of applying the present techniques in film applications, it is preferred that at least one of R ¹ or R ^2, to choose a group represented by the formula (2). Here, the polymerizable group represented by the formulas (PG-1) to (PG-8) can be appropriately selected depending on the production conditions of the film. However, in the case of producing a photo-curing film which is usually used, it is preferable to select the acrylic group or methacryl group represented by the formula (PG-1) to have high curability, solubility in solvents, low crystallinity, In view of the above.

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

(11)

(3) and (4), Z ³ is independently a single bond, -COO- or -COS-, Z ⁴ is each independently a single bond, -CH═CH-, -N═CH-, , -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- , or -C≡C-, and; R ⁵ is hydrogen, fluorine, chlorine, cyano, having 1 to 20 carbon atoms -CH ₂ - in the alkyl may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, and in the alkyl, hydrogen may be substituted with halogen A ⁴ is an aromatic ring of a monovalent, a 5-membered or 6-membered ring, or a condensed ring thereof, or a condensed ring thereof, and A ³ is a divalent aromatic ring, a 5-membered ring or a 6-membered aromatic ring, And at least one hydrogen in the aromatic rings or the condensed rings thereof in A ³ and A ⁴ is a substituent selected from the group consisting of fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, Alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, alkanoyl of 1 to 5 carbon atoms, And p is an integer of 0 to 2;

In order to lower or reverse the wavelength dispersibility of the refractive index anisotropy in the group represented by Q ¹ , it is more preferable that the group represented by the formula (4) is a group which imparts a high liquid crystallinity to the compound and the other liquid crystalline compound and the organic solvent , It is more preferable that Q ¹ is selected from the groups represented by the following formulas (4-1) to (4-9).

[Chemical Formula 12]

In the formulas (4-1) to (4-9), X ² is -O- or -S-, and at least one -CH═ may be substituted with -N═, and at least one hydrogen is fluorine , Chlorine, cyano, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms . * Represents the binding site.

Among the compounds represented by the above formula (1), from the viewpoints of good liquid crystallinity, low transparency, high solubility in organic solvents, high compatibility with other compounds, and the like, 1) to (1-1-21), (1-2-1) to (1-2-6), or (1-3-1) to (1-3-5) Is preferable.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In the formulas (1-1-1) to (1-3-5), R ¹ and R ² are each independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, Alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, alkyl ester of 1 to 20 carbon atoms, or a group represented by the following formula (2).

[Chemical Formula 19]

In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or alkylene having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -COO-, -OCO-, -CH = CH- or -C≡ C-; PG is a polymerizable group represented by any one of the following formulas (PG-1) to (PG-8).

[Chemical Formula 20]

In the formulas (PG-1) to (PG-8), R ⁴ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl. R ³ is hydrogen, alkyl, alkanoyl of 1 to 5 carbon atoms of 1 to 5 carbon atoms, R ⁵ is an alkyl of hydrogen, fluorine, chlorine, cyano, having a carbon number of 1~20, -CH ₂ in the alkyl-is -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, in the alkyl, hydrogen may be substituted with halogen, and R ⁶ is hydrogen, fluorine, chlorine , Alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, alkanoyl of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms Lt; / RTI >

The compound represented by the formula (1) of the present invention can be synthesized by combining known organic synthesis chemical methods. Methods for introducing the desired end groups, rings and bonding groups into the starting materials are described in Houben-Wyle (Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart), Organic Syntheses (John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Lectures (Maruzen) . The structure of the synthesized compound can be confirmed by, for example, a proton NMR spectrum.

<< Liquid Crystal Composition >>

The liquid crystal composition of the present invention contains at least one compound selected from the group of compounds represented by formula (1). The liquid crystal composition of the present invention has a nematic phase or a smectic phase liquid crystal phase at a relatively low temperature. When the liquid crystal composition of the present invention is coated on a plastic substrate subjected to alignment treatment such as rubbing treatment or on a support substrate coated with a thin film of plastic, a homogeneous orientation or a hybrid alignment is obtained. When the below-described non-polymerizable or polymerizable optically active compound is added to the liquid crystal composition of the present invention, twist orientation is obtained. When a compound having a cardo structure or a monofunctional liquid crystal compound described later is added to the liquid crystal composition of the present invention, homeotropic alignment can be easily obtained.

As the component other than the compound (1), other liquid crystal compounds (excluding the polymerizable liquid crystal compound), other polymerizable liquid crystal compounds, surfactants, other polymerizable compounds (except for the polymerizable liquid crystal compound) A polymerization initiator, a photosensitizer, a chain transfer agent, an antioxidant, an ultraviolet absorber, a radical scavenger, a light stabilizer, an optically active compound, a silane coupling agent, a solvent and other additives, You may.

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

[Chemical Formula 21]

In the formula (LC), A ⁵ is independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl and naphthalene-2,6- And at least one hydrogen in said divalent group is selected from the group consisting of fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, Alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms; Z ⁵ is independently a single bond or alkylene having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF- or -C? C-, and at least one hydrogen may be substituted with halogen; b is an integer from 1 to 5; R ⁸ is each independently hydrogen, fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 10 carbon atoms or alkoxy of 1 to 10 carbon atoms , And at least one -CH ₂ - in the alkyl may be substituted with -CH = CH-.

Hereinafter, specific examples of the compound represented by the formula (LC) are shown.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

The liquid crystal composition of the present invention is a liquid crystal composition comprising 100% by weight of a total amount of at least one member selected from the group consisting of at least one compound selected from the group of compounds of the present invention represented by formula (1) and the known compound represented by formula (LC) , 1 to 90% by weight of the compound of the present invention represented by the formula (1) and 10 to 99% by weight of the compound represented by the formula (LC).

As other polymerizable liquid crystal compounds, compounds represented by the following formulas (M1) and (M2) are preferable.

(25)

In the above formulas (M1) and (M2), A ^M is each independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine- Diyl or fluorene-2,7-diyl, wherein at least one of the hydrogens is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, tri Fluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms; Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF _{2 O-, -OCF 2 -, -CH} 2 CH 2 -, -CF 2 CF 2 -, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- , or -C≡C-, and; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester; q is an integer of 1 to 4;

a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO-.

Here, when q is 2 or more, these A ^M and Z ^M may be different for each repeating unit.

In the compounds represented by the above formulas (M1) and (M2), a compound represented by the formula (M1) is more preferable, and in the formula (M1), A ^M is independently 1,4- -Cyclohexylene, but at least one of A ^M is 1,4-cyclohexylene and in said 1,4-phenylene or 1,4-cyclohexylene, at least one hydrogen is fluorine, chlorine, tri Fluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms; Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ - ; q is an integer of 1 or 2; X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is preferably a single bond, -O-, -COO-, -OCO- or -OCOO-.

Other polymerizable liquid crystal compounds may include a compound represented by the following formula (M3).

(26)

In the formula (M3), A ^M is each independently 1,4-phenylene or 1,4-cyclohexylene, wherein at least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl , Trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms ; Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF _{2 O-, -OCF 2 -, -CH} 2 CH 2 -, -CF 2 CF 2 -, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- , or -C≡C-, and; c and d are each an integer of 0 to 3, and 1? m + n? 4; a is an integer from 0 to 20; R ^M is hydrogen or methyl; Y ^M is a single bond, -O-, -COO-, -OCO- or -OCOO-. Here, when c and d are two or more, these A ^M and Z ^M may be different for each repeating unit.

The compound represented by the formula (M1) is a monofunctional polymerizable liquid crystal compound, and it is easy to control the liquid crystal temperature range, optical characteristics and orientation of the liquid crystal composition, and it is preferable that at least one of A ^M has 1,4- The compound is more easily controllable, such as the wavelength dispersion characteristics and the temperature range of the liquid crystal phase. The compound represented by the formula (M2) is a bifunctional polymerizable liquid crystal compound, and since the polymer has a three-dimensional structure, a hard polymer as compared with the compound represented by the formula (M1) having one polymerizable group do. The compound represented by the formula (M3) is a triblock polymerizable liquid crystal compound, which can also form a rigid network and becomes a harder polymer than a compound having one and two polymerizable groups. Hereinafter, the compounds represented by the formulas (M1), (M2) and (M3) and the compounds derived therefrom may be collectively referred to as the formula (M).

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

(27)

(28)

In the formulas (M1-1) to (M1-23), R ^M is independently hydrogen or methyl, and a is independently an integer of 1 to 12.

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

[Chemical Formula 29]

(30)

(31)

In the formulas (M2-1) to (M2-31), R ^M is independently hydrogen or methyl, and a is independently an integer of 1 to 12. When two or more a's are present in the formula, any two a's may be the same or different.

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

(32)

(33)

In the formulas (M3-1) to (M3-10), R ^M is independently hydrogen or methyl, and a is independently an integer of 1 to 12. When two or more a's are present in the formula, any two a's may be the same or different.

The polymerizable liquid crystal composition of the present invention comprises at least one compound selected from the group of compounds of the present invention represented by formula (1) and at least one compound selected from the group of compounds represented by formulas (M1) and (M2) By weight of at least one compound selected from the group of the compounds of the present invention represented by the formula (1), based on 100% by weight of the total amount. When the content of each of the above components in the liquid crystal composition is in the above-mentioned range, it is possible to obtain a liquid crystal composition which is easy to control wavelength dispersion of refractive index anisotropy and which has good coating properties and can remarkably exhibit the effect of the polymer of the present invention have.

Further, it may further contain a compound represented by the formula (LC) or the formula (M3).

The liquid crystal composition of the present invention may further comprise a surfactant. As the surfactant, a nonionic surfactant is preferable. When a nonionic surfactant is included in the liquid crystal composition, the smoothness of the coating film formed of the liquid crystal composition is improved.

When the nonionic surfactant is added, the preferable ratio is the weight of the compound represented by the formula (1), and when the other liquid crystal compound or other polymerizable liquid crystal compound is contained, the compound represented by the formula (1) Is 0.0001 to 0.5 in terms of the weight ratio with respect to the total weight. A more preferable range of the weight ratio is 0.0001 to 0.005.

Examples of the nonionic surfactant include silicone-based nonionic surfactants, fluorine-based nonionic surfactants, and hydrocarbon-based nonionic surfactants.

Examples of commercial products of silicone-based nonionic surfactants include polyflow ATF-2, Glanol 100, Glanol 115, Glanol 400 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) , POLYFLOW KL-260, POLYFLOW KL-270, POLYFLOW KL-280, BYK-300, GLYNOL 410, GLONOL 435, GLONOL 440, GLONOL 450, GLONOL B- , BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK- -377, BYK-341, BYK-342, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, , BYK-3510, and BYK-3570.

Examples of commercially available fluorine-based nonionic surfactants include BYK-340, POTGENT 251, POTGENT 221MH, POTGENT 250, FTX-215M, FTX-218M, FTX-233M, FTX-245M, FTX- FTX-218G, FTX-240G, FTX-206D, PtGent 212D, FTX-218, FTX-220D, FTX-230D, FTX-213F, FTX-213F, PtGent 222F, FTX-233F, FTX-245F, FTX- , FTX-240D, FTX-720C, FTX-740C, FTX-207S, FTX-211S, FTX-220S, FTX-230S, KB-L82, KB-L85, KB-L97, KB- -F2L, KB-F2M, KB-F2S, KB-F3M, and KB-FaM.

As commercially available products of the hydrocarbon-based nonionic surfactants, for example, Polyflow No. 3, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, 354, BYK-355, BYK-358N, BYK-361N, BYK-351, BYK- 380N, BYK-381, BYK-392, and BYK-Silclean3700.

The above polyflow and glanol are all trade names of products sold by Kyowa Chemical Industry Co., Ltd. BYK is the name of a product sold by Big Chem Japan Co., Ltd. Phtagent, FTX and KB are the names of the products sold by Neos.

The above-mentioned surfactants may 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 products.

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

The other polymerizable compound may be added as long as it can retain the liquid crystal phase. When the weight of the compound represented by the formula (1) and other liquid crystal compounds or other polymerizable liquid crystal compounds are contained, the weight ratio of the compound to the total weight of the compound represented by the formula (1) is preferably 0.5 or less.

Examples of the compound having one polymerizable group include styrene, nuclear substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, ), alpha, beta -ethylenically unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid), alkyl esters of (meth) acrylic acid (C1 to C18 of hydroxyalkyl), aminoalkyl ester of (meth) acrylic acid (having 1 to 18 carbon atoms of aminoalkyl), ether oxygen-containing alkyl ester of (meth) acrylic acid Such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, and butylcarbyl ester), N-vinylacetamide, p-tert- butyl Benzo Vinyl benzoate, vinyl pivalate, vinyl 2,2-dimethylbutyric acid, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butylacetate, vinyl propionate, stearic acid (Meth) acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid, 2- acryloyloxyethyl hexahydrophthalic acid, Acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, Polyethylene glycol, polypropylene glycol (Meta) acrylic acid esters or di (meth) acrylic acid esters of polyalkylene glycols such as a copolymer of ethylene oxide and propylene oxide, or a polymerization degree capped by an alkyl group having 1 to 6 carbon atoms (Meth) acrylic acid esters of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide.

Examples of the compound having two polymerizable groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethyl Triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO-added diacrylate, bisphenol A glycidyldiacrylate (VISCOT V # 700), polyethylene glycol diacrylate, and methacrylate compounds of these compounds.

Examples of the compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol EO added tri (meth) acrylate, tris (meth) (Meth) acryloyloxyethyl isocyanurate, alkyl-modified dipentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethyl (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meta) acrylate, dipentaerythritol tetra ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, bis Coat V # 802 (number of functional groups = 8), Viscot V # 1000 (number of functional groups = 14), and the like. "Viscot" is a trade name of Osaka Organic Chemical Co., Ltd. The functional groups of 16 or more are obtained by acrylating them using Boltorn H20 (16-functional), Boltorn H30 (32-functional) and Boltorn H40 (64-functional), which are sold by Perstorp Specialty Chemicals.

Examples of other polymerizable compounds include polymerizable fluorene derivatives having a cardo structure. These compounds are suitable for controlling the orientation direction and further increasing the degree of curing of the polymer. Examples of polymerizable fluorene derivatives having a cardo structure are shown by the following formulas (? -1) to (? -6).

(34)

As the other polymerizable compound, a polymerizable compound having a bisphenol structure is exemplified. These compounds are suitable for assisting the film-forming ability and orientation uniformity of the liquid crystal composition. Examples of polymerizable bisphenol derivatives are represented by the following formulas (N-1) to (N-6).

(35)

The above other polymerizable compounds may be used alone, or two or more of them may be used in combination. These compounds may also be commercially available products.

In order to optimize the polymerization rate, a polymerization initiator may be added to the liquid crystal composition. As the polymerization initiator, for example, there is a photo radical initiator. Examples of the photo radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- (Irgacure 651), 1 -hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 Benzophenone mixture), Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800 , Irgacure 1850, Irgacure 1870, Darocure 4265, Darocure MBF, Darocure TPO, Irgacure 784, Irgacure 754, Irgacure OXE01, Irgacure OXE02, and the like. The above-mentioned DARACURE and IRGACURE are all the names of the products sold by BASF Japan Co., Ltd.

Examples of the photo radical polymerization initiator include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl- (4-isopropylphenyl) -2 (4-isopropylphenyl) -2, 4-isopropylphenoxypyridine, 2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) / p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture, and the like.

The amount of the photo-radical polymerization initiator to be added is preferably in the range of from 1 to 100 parts by weight based on the weight of the compound represented by the formula (1) and the total weight of the liquid crystal compound or other polymerizable liquid crystal compound and the compound represented by the formula (1) Lt; / RTI &gt; A more preferable range of the weight ratio is 0.001 to 0.15. A more preferred range is 0.01 to 0.15. The photoradical initiator may be used alone or in admixture of two or more. These polymerization initiators may be commercially available products.

A sensitizer may be added to these photo radical polymerization initiators. Examples of the sensitizer include isopropyl thioxanthone, diethyl thioxanthone, ethyl-4 dimethylaminobenzoate (Darocure EDB), 2-ethylhexyl-4-dimethylaminobenzoate (Darocure EHA) . These sensitizers may be used alone or in combination of two or more. These sensitizers may also be commercially available products.

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

Examples of the thiol chain transfer agent include monofunctional thiol such as dodecanethiol, 2-ethylhexyl-3-mercaptopropionate and the like, and trimethylolpropane tris (3-mercaptopropionate), which is a multifunctional thiol, Pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (carboxy MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) Carboxylactone MT PE1), and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) Lens MT NR1), and the like. &Quot; Car lens &quot; is a trade name of Showa Denko KK.

Examples of the styrene dimer-based 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 in order to prevent polymerization initiation at the time of storage. (BHT), hydroquinone, methylene blue, diphenyl picric acid hydrazide (DPPH), phenothiazine (DPPH), or the like can be used. , And N, N-dimethyl-4-nitrosoaniline, benzothiazine derivatives such as o-hydroxybenzophenone and 2H-1,3-benzothiazin-2,4- to be.

In order to improve the preservability of the liquid crystal composition, a polymerization inhibitor may be added. When a radical is generated in the liquid crystal composition or the liquid crystal composition solution, the polymerization reaction of the polymerizable compound is promoted. It is preferable to add a polymerization inhibitor for the purpose of preventing this. 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 ultraviolet absorbers 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, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, Adecastab LA- 34, adecastab LA-36, adecastab LA-31, adecastab 1413, and adecastab LA-51. "Tinuvin" is a trade name of BASF Japan Ltd., and "Adekastab" is a trade name of ADEKA. These ultraviolet absorbers may be used alone or in admixture of two or more. These ultraviolet absorbers may be commercially available products.

Examples of the light stabilizers include Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, 5100, Tinuvin 5050, 5060, Tinuvin 5151, KIMASOV 119FL, KIMASOV 944FL, KIMASOV 944LD, Adecastab LA-52, Adecastab LA-57, Adecastab LA- Adabsorption LA-67, Adecastab LA-63P, Adecastab LA-68LD, Adecastab LA-77, Adecastab LA-82, Adecastab LA-87, 3346, and Goodrich UV-3034 from Goodrich. &Quot; KIMASOV &quot; is a trade name of BASF Japan Co., Ltd. These light stabilizers may be used alone or in combination of two or more thereof. These light stabilizers may be commercially available products.

As the antioxidant, for example, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 of ADEKA, Sumilizer BHT sold by Sumitomo Chemical Co., Irganox1010, Irganox3114, and Irganox245 sold by BASF Japan Co., Ltd., and the like. These antioxidants may be used alone or in admixture of two or more. These antioxidants may be commercially available products.

A silane coupling agent may be added to the liquid crystal composition for the purpose of controlling the adhesion with the substrate or the like. Examples of the silane coupling agent include vinyltrialkoxysilane, 3-isocyanatopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene ) Trialkoxysilyl) -1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxy And silane. Further, dialkoxymethylsilane in which one of the alkoxy groups (3) in the alkoxysilane is substituted with methyl can also be used as a silane coupling agent. These silane coupling agents may be used alone or in admixture of two or more. These silane coupling agents may be commercially available products.

The liquid crystal composition of the present invention is prepared by diluting the liquid crystal composition using a solvent or dissolving each component of the liquid crystal composition in a solvent to prepare a solution of a liquid crystal composition comprising a liquid crystal composition and a solvent, This solution may be applied. Examples of the solvent include ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents Solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

Examples of the ester solvent include alkyl acetates such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate, ethyl trifluoroacetate , Alkyl propionates such as methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate, alkyl butyrates such as methyl butyrate, butyl butyrate, isobutyl butyrate and butyrate propyl, Alkyl alcohols such as methyl lactate, diethyl malonate, alkyl glycolates such as methyl glycolate and ethyl glycolate, alkyl lactates such as methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, Ethylhexyl), monoacetin,? -Butyrolactone and? -Valerolactone, and the like are preferable.

Examples of the amide solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N- Diethylacetamide, N, N-dimethylacetamide dimethylacetal, N-methylcaprolactam, and dimethylimidazolidinone are preferable.

Examples of the alcohol solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, tert -butyl alcohol, sec-butyl alcohol, Propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, Ethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, - pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and methylcyclohexanol are preferred.

As the ether solvent, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane and tetrahydrofuran (THF) are preferable.

Examples of the glycol monoalkyl ether solvents include ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ethers (e.g., diethylene glycol monoethyl ether), triethylene glycol mono Alkyl ethers such as propylene glycol monoalkyl ethers such as propylene glycol monobutyl ether, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate ), Diethylene glycol monoalkyl ether acetates (e.g., diethylene glycol monoethyl ether acetate), triethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates (e.g., propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate and Propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (e.g., dipropylene glycol monomethyl ether acetate), and diethylene glycol methyl ethyl ether.

Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, tert-butylbenzene, sec- It is Lin. Preferable examples of the halogenated aromatic hydrocarbon solvents are chlorobenzene and the like. As the aliphatic hydrocarbon solvent, hexane, heptane and the like are preferable. As the halogenated aliphatic hydrocarbon solvent, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene and the like are preferable. As the alicyclic hydrocarbon solvent, cyclohexane and decalin are preferable.

As the ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like are preferable.

As the acetate solvent, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate and the like are preferable.

From the viewpoint of the solubility of the liquid crystal compound, it is preferable to use an amide type solvent, an aromatic hydrocarbon type or a ketone type solvent. In consideration of the boiling point of the solvent, ester type solvents, alcohol type solvents, ether type solvents, glycol monoalkyl It is also preferable to use an ether type solvent in combination. There is no particular limitation on the choice of the solvent. However, when a plastic substrate is used as the substrate, it is necessary to lower the drying temperature and prevent the substrate from eroding the substrate in order to prevent deformation of the substrate . The solvent preferably used in this case is an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, an acetate solvent or a glycol monoalkyl ether solvent.

The proportion 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. A preferable range of this ratio is 10 to 50 wt%, and a more preferable range is 10 to 40 wt%. These solvents may be used alone or in admixture 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 is sometimes referred to as a liquid crystal film. The liquid crystal film can be obtained as follows. First, the 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 nematic alignment formed in the liquid crystal state of the composition in the coating film is fixed. Examples of the material of the usable support substrate include glass and plastic. Examples of the plastic include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate Polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetylcellulose and its partial saponification, epoxy resin, phenolic resin, and Cycloolefin-based resins, and the like. The supporting substrate is usually a sheet or film type.

Examples of the cycloolefin-based resin include norbornene-based resins and dicyclopentadiene-based resins, but are not limited thereto. Of these, those having no unsaturated bond or having an unsaturated bond hydrogenated are preferably used. For example, hydrogenated products of ring-opening (co) polymers of one or more norbornene monomers, addition (co) polymers of one or more norbornene monomers, copolymers of norbornene monomers and olefin monomers ( An addition copolymer of a norbornene monomer and a cycloolefin monomer (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and a modified product thereof Specific examples thereof include ZEONEX, ZEONOR (all trade names, manufactured by Nippon Zeon), ARTON (trade name, manufactured by JSR Corporation), TOPAS (trade name, manufactured by Tico Corporation), APEL (Trade name, manufactured by Sekisui Chemical Co., Ltd.) and OPTOREZ (trade name, manufactured by Hitachi Chemical Co., Ltd.).

These plastic films (plastic films) which can be used as support substrates may be uniaxially stretched films or biaxially stretched films. These films may be subjected to surface treatment such as hydrophilization treatment such as corona treatment or plasma treatment or hydrophobic treatment. The hydrophilization treatment method is not particularly limited, but a corona treatment or a plasma treatment is preferable, and a particularly preferable method is a plasma treatment. As the plasma treatment, a method described in Japanese Unexamined Patent Application Publication No. 2002-226616 and Japanese Unexamined Patent Publication No. 2002-121648 may be used. An anchor coating layer may be formed to improve the adhesion between the liquid crystal film and the plastic film. Such an anchor coating layer may be either an inorganic material or an organic material as long as it enhances adhesion between the liquid crystal film and the plastic film. The plastic film may be a laminated film. Instead of the plastic film, a metal substrate such as aluminum, iron, or copper having a slit-shaped groove formed on its surface, or a glass substrate such as alkali glass, borosilicate glass, or lead glass whose surface has been subjected to a slit etching process may be used.

When a liquid crystal film of a homogeneous orientation or a hybrid orientation is formed on a support substrate such as a glass substrate or a plastic film prior to the formation of the coating film of the liquid crystal composition, physical and mechanical surface treatment by rubbing or the like is performed. In the case of forming a liquid crystal film of homeotropic orientation, surface treatment such as rubbing is often not performed, but rubbing treatment can also be performed in order to prevent alignment defects and the like. Any method can be employed for the rubbing treatment, but usually a method in which a rubbing cloth made of a material such as rayon, cotton or polyamide is wound on a metal roll or the like, and the roll is rotated while being in contact with the support substrate or the polymer film , A method of moving the support substrate side on which the roll is fixed, and the like. The rubbing treatment may be carried out directly on the support substrate, or a polymer film such as polyimide, which is generally referred to as an orientation film, may be formed on the support substrate in advance, and the polymer film may be rubbed. The rubbing treatment method is as described above. Depending on the type of the support substrate, the silicon oxide may be deposited on the surface of the support substrate in an oblique manner to give the alignment ability.

In addition, in the case of forming a liquid crystal film of homogeneous alignment and hybrid alignment, in addition to performing physical and mechanical surface treatment by rubbing or the like, polyimide, polyacrylate, or the like, which is generally called a photo alignment film, And a polarizing UV treatment may be applied to the polymer coating.

Examples of a coating method for obtaining a uniform film thickness when applying the liquid crystal composition or its solution include spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dipping coating method, spray coating A meniscus coating method, and a die coating method. In particular, it may be used in a case where the orientation of the liquid crystal composition is controlled without performing surface treatment of the substrate by rubbing or the like, such as a wire bar coating method in which a shearing stress is applied to a liquid crystal composition at the time of application.

When applying the solution of the liquid crystal composition of the present invention, heat treatment may be performed after the application to form a polymerizable liquid crystal layer, that is, a liquid crystal composition layer having a uniform film thickness on the support substrate. As the heat treatment, a hot plate, a drying furnace, hot air or hot air spraying can be used.

The temperature and time at the time of heat treatment of the coating film, the wavelength of light used for light irradiation, the amount of light irradiated from the light source, and the like depend on the type and composition ratio of the compound used in the liquid crystal composition, the presence or absence of addition of a photopolymerization initiator, The preferred ranges are different. Therefore, the conditions for the temperature and time of the heat treatment of the coating film, the wavelength of the light used for the light irradiation, and the amount of the light irradiated from the light source, which will be described below,

The heat treatment of the coating film is preferably performed under a condition that uniform orientation of the polymerizable liquid crystal can be obtained. But may be performed at a liquid crystal phase transition point or more of the liquid crystal composition. One 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 to form a nematic orientation in the liquid crystal composition in the coating film. The nematic orientation may be formed by changing the temperature of the coating film within a temperature range in which the liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which a nematic orientation is almost completed in the coating film by warming the coating film to a high temperature region within the above-mentioned temperature range, and then the temperature is lowered to make the orientation more orderly. In any of the heat treatment methods described above, the heat treatment temperature is from room temperature to 120 占 폚. The preferable range of the temperature is from room temperature to 80 deg. C, more preferably from room temperature to 60 deg. The heat treatment time is 5 seconds to 2 hours. The preferred range of this time is from 10 seconds to 40 minutes, more preferably from 20 seconds to 20 minutes. In order to raise the temperature of the layer made of 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 lower the productivity, it is preferable to set the heat treatment time within 2 hours. Thus, the polymerizable liquid crystal layer of the present invention can be obtained.

The nematic alignment state of the liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by polymerizing this liquid crystal compound by light irradiation. The wavelength of light used for light irradiation is not particularly limited. An electron beam, an ultraviolet ray, a visible ray, and an infrared ray (hot line). Usually, ultraviolet rays or visible rays may be used. The wavelength ranges from 150 to 500 nm. A preferable range is 250 to 450 nm, and a more preferable range is 300 to 400 nm. Examples of light sources are low pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), 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) . Preferable examples of the light source include a metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp, and a high-pressure mercury lamp. A wavelength region of the irradiation light source can also be selected by passing a specific wavelength region through a filter or the like between the light source and the polymerizable liquid crystal layer. The amount of light irradiated from the light source is ² to 5000 mJ / cm &lt; ² &gt; A preferable range of the light amount is 10 to 3000 mJ / cm ² , and a more preferable range is 100 to 2000 mJ / cm ² . The temperature condition at the time of light irradiation is preferably set equal to the above-mentioned heat treatment temperature. The atmosphere of the polymerization environment may be any one of a nitrogen atmosphere, an inert gas atmosphere, and an air atmosphere, but a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving curability.

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 for use in liquid crystal display devices, It becomes extremely important to control the distribution.

One of the methods for controlling the tilt angle is a method of adjusting the kind, the 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 be controlled also by the kind of the solvent in the liquid crystal composition, the concentration of the solute, and the type and amount of the surfactant to be added as another component. The tilt angle of the liquid crystal film can be controlled also by the kind of the support substrate or the polymer film, the rubbing condition, the drying condition of the coating film of the liquid crystal composition, the heat treatment condition and the like. In addition, the irradiation atmosphere and the temperature at the time of irradiation in the photopolymerization step after orientation also affect the tilt angle of the liquid crystal film. That is, almost all conditions in the manufacturing process of the liquid crystal film may be considered to affect the tilt angle even slightly. Accordingly, arbitrary tilt angle can be obtained by appropriately selecting various conditions of the liquid crystal film production process together with optimization of the liquid crystal composition.

The homogeneous orientation is such that the tilt angle is uniformly distributed near 0 deg., Particularly 0 deg. To 5 deg., From the substrate interface to the free interface. This alignment state is obtained by applying the liquid crystal composition of the present invention to the surface of a support substrate subjected to a surface treatment such as rubbing to form a coating film.

A chiral compound, that is, a compound having optical activity, may be added to the liquid crystal composition of the present invention. Examples of suitable optically active compounds are compounds represented by the formulas (Op-1) to (Op-25). In these formulas, Ak represents an alkyl of 1 to 15 carbon atoms or an alkoxy of 1 to 15 carbon atoms, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. P ² is a polymerizable group, and is preferably a group containing (meth) acryloyloxy, vinyloxy, oxiranyl, or oxetanyl. The liquid crystal composition of the present invention can be used as a liquid crystal which is a component of a liquid crystal display element, in addition to being used as a raw material of the polymer described below.

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As a specific example, there is one described in paragraph 0170 of paragraphs 0159 to 81 in p. 70 of Japanese Laid-Open Patent Publication No. 2011-148762.

A liquid crystal composition containing an optically active compound in an appropriate amount or a liquid crystal composition containing an optically active polymerizable compound in an appropriate amount is coated on a substrate subjected to orientation treatment and polymerized to form a retardation film exhibiting a helical structure Can be obtained. By polymerization of the liquid crystal composition, this helical structure is fixed. The properties of the resulting liquid crystal film depend on the helical pitch of the obtained helical structure. The length of the helix pitch can be adjusted by the kind of the optically active compound and the addition amount. There may be only one optically active compound to be added, but a plurality of optically active compounds may be used for the purpose of canceling the temperature dependency of the helical pitch. In addition to the optically active compound, the liquid crystal composition may contain other polymerizable compounds.

The selective reflection of visible light, which is a characteristic of the liquid crystal film, is such that the helical structure acts on incident light and reflects circularly polarized light or elliptically polarized light. Since the selective reflection characteristic is represented by λ = n · Pitch (λ is the central wavelength of selective reflection, n is the average refractive index, and Pitch is the helical pitch), the center wavelength λ and the wavelength width Δλ are changed by changing n or Pitch Can be adjusted appropriately. In order to improve the color purity, the wavelength width DELTA lambda can be made small, and when the wide band reflection is desired, the wavelength width DELTA lambda can be made large. This selective reflection is also greatly influenced by the thickness of the polymer. In order to maintain color purity, the thickness should not be too small. In order to maintain uniform orientation, the thickness must not be excessively large. Therefore, it is necessary to adjust the thickness appropriately, preferably 0.5 to 25 탆, more preferably 1 to 10 탆.

Negative C plate (Negative C plate) described in W. H. de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared by making the spiral pitch shorter than visible light. In order to shorten the helical pitch, it can be achieved by using an optically active compound having a large twisting force (HTP: helical twisting power) and increasing the addition amount thereof. Concretely, by setting λ to 350 nm or less, preferably 200 nm or less, a negative C plate can be prepared. This negative type C plate is an optical compensation film suitable for a display element such as a VAN type, a VAC type or an OCB type of liquid crystal display element.

The liquid crystal film can be used for a reflective film whose reflection wavelength range described in Japanese Laid-Open Patent Publication No. 2004-333671 is set to near infrared (wavelength 800 to 2500 nm) by making the spiral pitch longer than visible light. In order to lengthen the spiral pitch, for example, it can be achieved by using an optically active compound having a small twisting force or by decreasing the amount of the optically active compound to be added.

The optically active compound may be any optically active compound as long as it can induce the helical structure and suitably mix with the liquid crystal composition serving as the base. Further, any of the polymerizable compound and the non-polymerizable compound may be used, and an optimum compound may be added according to the purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is preferable.

Among the above-mentioned optically active compounds, a larger twist force (HTP: helical twisting power) is preferable for shortening the helical pitch. Representative examples of compounds having a large twisting force are disclosed in GB 2298202 and DE 10221751.

The thickness (film thickness) of the liquid crystal film is different depending on the retardation depending on the intended device or the birefringence (optical anisotropy value) of the liquid crystal film. Therefore, although the range of the thickness varies from purpose to purpose, the standard is 0.05 to 100 mu m. A more preferred range is 0.1 to 50 占 퐉, and a more preferable range is 0.5 to 20 占 퐉. A preferable haze value of the liquid crystal film is 1.5% or less, and a preferable transmittance is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. It is preferable that the transmittance satisfies these conditions in the visible light region.

As the birefringence (the value of optical anisotropy) of the liquid crystal film is higher, the thickness can be reduced. The thinner the thickness, the better the optical characteristics such as the haze value and the transmittance tend to become better.

The liquid crystal film is effective as an optical compensation element applied to a liquid crystal display element (in particular, an active matrix type and a passive matrix type liquid crystal display element). Examples of the liquid crystal display element type suitable for using this liquid crystal film as an optical compensation film include IPS type (in-plane switching), OCB type (optically compensated birefringence), TN type (twisted nematic) (Super twisted nematic), ECB type (electrically controlled birefringence), DAP type (deformation effect of alignment phase), CSH type (color super-homeotropic), VAN / VAC Type (nematic / cholesteric), OMI type (optical mode interference), SBE type (super birefringence effect), and the like. The liquid crystal film may also be used as a phase retarder for a display element such as a guest-host type, a ferroelectric molding, or an anti-ferroelectric molding. The optimal values of the parameters such as the thickness distribution in the thickness direction and the thickness required for the liquid crystal film depend strongly on the type of the liquid crystal display element to be compensated and the optical parameters thereof,

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 disposed outside the liquid crystal cell. On the other hand, the liquid crystal film as the optical compensation element can be disposed inside the liquid crystal cell, since there is little or no elution of impurities into the liquid crystal filled in the cell. For example, by applying the method disclosed in Japanese Patent Application Laid-Open No. 2008-01943, it is possible to further improve the function of the color filter by forming the polymerizable liquid crystal layer of the present invention on the color filter. There is no particular limitation on the type of the polarizer used for the optical element to which the liquid crystal film can be applied, and there is no particular limitation on the polarizing plate of the absorbing type doped with iodine which is widely used, and the optical compensation of the reflective polarizing plate such as the wire grid polarizing plate Can be preferably used.

The liquid crystal film may contain an additive such as a dichroic dye. As the dichroic dye, a dye comprising anthraquinone, naphthoquinone or azobenzene is preferable. The liquid crystal film of the homogeneous orientation in which the dichroic dye and the dichroic dye are combined can also be used as an absorption type polarizing plate. Further, a homogeneous liquid crystal film composed of a fluorescent dye combined with a fluorescent dye can also be used as a polarized light emitting type film.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

&Lt; Identification of Structure of Compound &

The structure of the compound synthesized by measurement of proton NMR (Bruker: DRX-500) at 500 MHz was confirmed. The numerical values are expressed in ppm, s is singlet, d is doublet, t is triplet, and m is multiplet.

<Phase transition temperature>

A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and the temperature was raised at a rate of 3 ° C / minute. The temperature at which the phase migrates to the other phase was measured. C means crystal, N means nematic phase, S means Smectic phase, and I means isotropic liquid. The NI point is the upper limit temperature in the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. &Quot; C 50 N 63 I &quot; indicates transition from crystal to nematic phase at 50 ° C and transition from a nematic phase to an isotropic liquid at 63 ° C. The parentheses indicate the liquid crystal phase of a monotropic peak.

<Polymerization Conditions>

Under a nitrogen atmosphere, light of 30 mW / cm ² (365 nm) was irradiated for 30 seconds using a 250 W ultra-high pressure mercury lamp at room temperature (Multilight-250 manufactured by Wuxi Mining Co., Ltd.).

&Lt; Evaluation of orientation >

(1) Production of a glass substrate on which a rubbed alignment film is formed

Polyamic acid (Rixson aligner: PIA-5370 JNC) for low tilt angle (horizontal alignment mode) was spin-coated on a glass substrate having a thickness of 1.1 mm, and the solvent was hot-rolled from a coating film obtained by spin coating at 80 占 폚 After removal on the plate, the coating film was fired in an oven at 230 DEG C for 30 minutes, and then rubbed with a rayon cloth.

(2) Visual observation method

A substrate on which a retardation film was formed was observed between two polarizing plates arranged in a crossed Nicols state, and the substrate was rotated in a horizontal plane to check the contrast state. The substrate on which the retardation film was formed was observed with a polarizing microscope to confirm the presence of alignment defects.

(3) Measurement by a polarization analyzer

Using a OPTIPRO polarization analyzer manufactured by Shin-Tek Co., a substrate having a retardation film formed thereon was irradiated with light having wavelengths of 550 nm and 450 nm. And the retardation was measured while reducing the angle of incidence of these lights from 90 DEG with respect to the film surface. The retardation (retardation) is expressed as [Delta] nxd. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

&Lt; Measurement of film thickness &

The layer of the liquid crystal film of the glass substrate on which the liquid crystal film was adhered was scratched off and the step was measured using a fine shape measuring device (Alpha Step IQ manufactured by KLA TENCOR Co.).

<Evaluation of optical anisotropy (? N)

(N) = retardation (Re) / film thickness (d) from the retardation and the film thickness value when the angle of incidence of light obtained with respect to the liquid crystal film having the homogeneous orientation is 90 DEG with respect to the film surface Respectively.

&Lt; Evaluation of wavelength dispersion characteristics >

As a characteristic of the wavelength dispersion, a value obtained from the following equation was taken as an index.

Characteristics of wavelength dispersion = retardation (Re _{450 nm} ) measured with light at 450 nm / retardation (Re _{550 nm} ) measured with light at 550 nm.

That is, when the characteristic value of the wavelength dispersion is small, the low-wavelength dispersion property is high, and when the value is 1 or less, it has the reverse wavelength dispersion characteristic.

<Pencil hardness>

And measured according to JIS standard "JIS-K-5400 8.4 Pencil scratching test" method. That is, a pencil (Mitsubishi Pencil Co., Ltd.) Uni fixed at an angle of 45 ° was scratched using a pencil hardness tester (Yoshimitsu Precision Machinery Co., Ltd., C-221) to measure the hardness of the pencil lead at the time of occurrence of the scratch.

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

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Compound (ex-1) can be prepared according to Heterocyclic specifications. 8, 2, 135 (2002).

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

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

The phase transition temperature and NMR analysis value of the obtained compound (1-1-2-1) are as follows.

Phase transition temperature (캜): C 95 I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.96 (s, 1H), 7.28 (d, 1H), 7.17 (d, 1H), 3.92 (s, 3H), 2.65-2.55 (m, 2H), 2.22 ( d, 4H), 1.92 (d, 4H), 1.68-1.57 (m, 4H), 1.38-1.19 (m, 18H), 1.07-0.97 (m, 4H), 0.90 (t, 6H).

[Example 2]

The following compound (1-1-19-1) was synthesized as follows.

[Chemical Formula 39]

The compound (ex-3) can be prepared according to Heterocyclic specifications. 8, 2, 135 (2002).

5.0 g of the compound (ex-3), 2.0 g of phenol and 0.5 g of DMAP were added to 50 mL of dichloromethane, and the mixture was stirred under cooling in a nitrogen atmosphere. Then, 10 mL of a DCC 4.5 g dichloromethane solution was added dropwise. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene) and recrystallized from methanol to obtain 4.8 g of compound (ex-4).

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

4.2 g of the compound (ex-5) was added to 42 mL of ethanol, and the mixture was stirred at 10 DEG C or lower under a nitrogen atmosphere. To this, 1.3 g of sodium borohydride was added. Thereafter, the mixture was stirred at 10 DEG C or lower for 3 hours. To the reaction mixture was added 40 mL of 1 N hydrochloric acid, and then 40 mL of water was added. The precipitate was filtered and washed with a large amount of water to obtain 4.0 g of Compound (ex-6).

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

The phase transition temperature and NMR analysis value of the obtained compound (1-1-19-1) are as follows.

Phase transition temperature (캜): C 110 I

_{^{1 H-NMR (CDCl 3;}} δppm): 8.08 (s, 1H), 7.45 (t, 2H), 7.31 (d, 2H), 7.27-7.22 (m, 2H), 7.19 (d, 1H), 2.65- 2H), 2.22 (d, 4H), 1.92 (d, 4H), 1.69-1.58 (m, 4H), 1.36-1.19 (m, 18H), 1.07-0.97 t, 6H).

[Example 3]

The following compound (1-1-7-1) was synthesized as follows.

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The compound (ex-7) can be prepared according to Heterocyclic specifications. 8, 2, 135 (2002).

5.0 g of the compound (ex-7), 3.2 g of benzyl mercaptan and 2.9 g of potassium hydroxide were added to 50 ml of N, N-dimethylformamide (DMF) and stirred for 4 hours while heating at 100 占 폚 in a nitrogen atmosphere. Water was poured into the reaction solution, the precipitate was filtered, and washed with water and methanol. The crystals thus obtained were recrystallized from a mixed solution of toluene and methanol to obtain 3.5 g of the compound (ex-8).

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

1.4 g of the compound (ex-9) was added to ethanol (14 mL), and the mixture was stirred at 10 ° C or lower under a nitrogen atmosphere. To this, 0.5 g of sodium borohydride was added. Thereafter, the mixture was stirred at 10 DEG C or lower for 3 hours. 14 mL of 1N hydrochloric acid was added to the reaction solution, and then 14 mL of water was added. The precipitate was filtered and washed with a large amount of water to obtain 1.0 g of Compound (ex-10).

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

25.0 g of trans-4-hydroxycyclohexanecarboxylic acid and 26.3 g of triethylamine were added to 125 mL of DMF, and the mixture was stirred while being cooled at 10 ° C or lower in a nitrogen atmosphere. Thereto, 14.7 g of chloromethyl methyl ether was slowly added dropwise. After dropwise addition, the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added to extract the organic layer, and the organic layer was washed with saturated aqueous sodium bicarbonate and water, and dried over anhydrous magnesium sulfate. The ethyl acetate was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 2/1) 25.2 g.

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

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

25.2 g of the compound (ex-14) and 11.0 g of triethylamine were added to 252 mL of dichloromethane, and the mixture was stirred while being cooled at 10 占 폚 or lower in a nitrogen atmosphere. To this, 8.3 g of acrylic acid chloride was slowly added dropwise. After dropwise addition, the mixture was stirred at room temperature for 8 hours. Water was added to extract the organic layer, and the organic layer was washed with saturated aqueous sodium bicarbonate and water, and dried over anhydrous magnesium sulfate. The dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 14/1)) and dried under reduced pressure. The obtained residue and 0.9 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 35 mL of THF and 17.5 mL of 2-propanol (IPA), and the mixture was heated and stirred at 40 DEG C for 8 hours. Ethyl acetate and water were added to extract the organic layer, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of ethyl acetate and heptane to obtain 7.4 g of compound (ex-15).

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

The phase transition temperature and NMR analysis values of the obtained compound (1-1-7-1) are as follows.

Phase transition temperature (캜): C 62 I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.69 (s, 2H), 7.46 (t, 2H), 7.41 (t, 1H), 7.36 (s, 1H), 7.26-7.20 (m, 2H), 6.44 ( (d, 2H), 6.19-6.12 (m, 2H), 5.86 (d, 2H), 4.88-4.80 m, 8H), 2.21-2.13 (m, 4H), 1.90-1.79 (m, 4H), 1.77-1.68 (m, 8H), 1.59-1.42 (m, 8H).

[Example 4]

The following compound (1-1-5-1) was synthesized as follows.

(41)

50.0 g of 4-hydroxybutyl acrylate, and 50 mL of pyridine were added to 150 mL of toluene, and the mixture was stirred at room temperature under a nitrogen atmosphere. Thereto was slowly added 72.8 g of tosyl chloride. Thereafter, the mixture was stirred at room temperature for 16 hours. Further, water was added and the mixture was heated and stirred at 40 占 폚 for 3 hours. The organic layer was extracted, washed with 5% aqueous hydrochloric acid and saturated aqueous sodium bicarbonate, and then with water, dried over anhydrous magnesium sulfate, and then toluene was distilled off under reduced pressure. 59.1 g of the obtained residue, hydroquinone and 148.0 g of potassium carbonate were added to 400 mL of DMF, and the mixture was stirred under heating in a nitrogen atmosphere at 80 占 폚 for 8 hours. Ethyl acetate and water were added and the organic layer was extracted. The organic layer was washed with a saturated aqueous layer of water and water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / 1)) to obtain 22.9 g of the compound (ex-16).

50.0 g of trans-cyclohexanedicarboxylic acid, and 38.1 g of potassium carbonate were added to DMF (250 mL), and the mixture was heated and stirred at 60 占 폚 in a nitrogen atmosphere. To this, 47.1 g of benzyl bromide was slowly added dropwise. After dropwise addition, the mixture was stirred at 80 占 폚 for 6 hours. Toluene and 3 N aqueous hydrochloric acid were added to extract the organic layer, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure to obtain 43.7 g of compound (ex-17).

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

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

7.7 g of the compound (ex-16), 7.1 g of the compound (ex-19) and 0.8 g of DMAP were added to 80 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. Then, 15 mL of a DCC solution of 7.0 g of dichloromethane was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and dried under reduced pressure. The obtained residue and 0.3 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 15 mL of THF and 7.5 mL of 2-propanol (IPA), and the mixture was heated and stirred at 40 占 폚 for 8 hours. Ethyl acetate and water were added to extract the organic layer, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a mixed solution of ethyl acetate and heptane to obtain 3.3 g of compound (ex-20).

1.0 g of the compound (ex-10) described in Example 3, 3.3 g of the compound (ex-20) and 0.2 g of DMAP were added to 40 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. 5 mL of a dichloromethane solution of 1.8 g of DCC was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized from methanol to obtain 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 (캜): C 129 N 180 <I

("180 < I" means that the transparent point can not be measured by polymerization at around 180 DEG C, but if not polymerized, it is expected that there will be a transition temperature from nematic phase to isotropic liquid at 180 DEG C or higher)

_{^{1 H-NMR (CDCl 3;}} δppm): 7.70 (d, 2H), 7.44 (t, 2H), 7.41-7.36 (m, 2H), 7.16-7.11 (m, 2H), 7.00 (d, 4H), 4H), 3.99 (t, 4H), 2.78-2.69 (m, 2H), 6.84 (d, 2H) 2H), 2.67-2.59 (m, 2H), 2.43-2.30 (m, 8H), 1.93-1.67 (m, 16H).

[Example 5]

The following compound (1-1-6-1) was synthesized as follows.

(42)

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

69.2 g of the compound (ex-21) and 44.1 g of dimethylaniline were added to 700 mL of toluene, and the mixture was stirred while being cooled at 10 DEG C or lower in a nitrogen atmosphere. Thereto, 28.2 g of acrylic acid chloride was slowly added dropwise. After the dropwise addition, the mixture was heated and stirred at 40 占 폚 for 4 hours. Water was added to extract the organic layer, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was recrystallized with toluene to obtain 50.0 g of Compound (ex-22).

42.9 g of the compound (ex-22), 25.2 g of the compound (ex-12) described in Example 3 and 3.3 g of DMAP were added to 430 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. Then, 60 mL of a dichloromethane solution of 29.0 g of DCC was added dropwise. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with saturated aqueous sodium hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. The dichloromethane was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 12/1)) and dried under reduced pressure. The obtained residue and 2.1 g of p-toluenesulfonic acid (pTSA) were added to a mixed solution of 110 mL of THF and 55 mL of IPA, and the mixture was heated and stirred at 40 占 폚 for 8 hours. Ethyl acetate and water were added to extract the organic layer, and 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 solvent of ethyl acetate and heptane to obtain 31.8 g of compound (ex-23).

3.2 g of the compound (ex-10) described in Example 3, 12.1 g of the compound (ex-23) and 0.7 g of DMAP were added to 40 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. 12 mL of a dichloromethane solution of 5.9 g of DCC was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized from methanol to obtain 1- 1-6-1).

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-1) are as follows.

Phase transition temperature (캜): C 90 (N 70) I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.67 (d, 2H), 7.44 (t, 2H), 7.38 (t, 1H), 7.33 (s, 1H), 7.15-7.08 (m, 6H), 6.83 ( 4H), 3.94 (t, 4H), 4.80 (d, 2H) 2H), 2.62 (t, 4H), 2.31-2.24 (m, 4H), 2.15-2.07 (m, 4H), 1.86-1.67 (m, 12H) , 1.56-1.41 (m, 12H).

[Example 6]

The following compound (1-1-6-2) was synthesized in the same manner as in Example 3, except that benzyl mercaptan was changed to 4-chlorobenzyl mercaptan.

(43)

The phase transition temperature and NMR analysis values of the obtained compound (1-1-6-2) are as follows.

Phase transition temperature (캜): C 90 (N 39) I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.60 (d, 2H), 7.41 (d, 2H), 7.30 (s, 1H), 7.15-7.08 (m, 6H), 6.82 (d, 4H), 6.40 ( 4H), 3.94 (t, 4H), 2.90 (t, 4H), 4.94 (m, 2H) , 2.72-2.58 (m, 6H), 2.31-2.23 (m, 4H), 2.15-2.07 (m, 4H), 1.86-1.67 (m, 12H), 1.56-1.42 (m, 12H).

[Example 7]

The following compound (1-1-15-1) was synthesized as follows.

(44)

5.0 g of the compound (ex-3) described in Example 2 and 0.02 mL of DMF were added to 30 mL of thionyl chloride, and the mixture was stirred under reflux for 1 hour under a nitrogen atmosphere. Thionyl chloride was distilled off under reduced pressure, toluene was added, and toluene was distilled off under reduced pressure. The resulting residue was added to 100 mL of THF and stirred at 10 DEG C or lower in a nitrogen atmosphere. Then, 2.6 g of 2-aminobenzenethiol was added dropwise thereto. After the dropwise addition, the mixture was stirred at 10 DEG C or lower for 1 hour, and 2.3 g of triethylamine was further added. After the addition, the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added and the organic layer was extracted. The organic layer was washed with saturated aqueous sodium hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. THF and ethyl acetate were distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluent: toluene-dichloromethane mixture (volume ratio: toluene / dichloromethane = 2/1)) and dried under reduced pressure, 24).

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

Compound (ex-25) (1.0 g) was added to ethanol (10 mL), and the mixture was stirred at 10 ° C or lower under a nitrogen atmosphere. To this, 0.3 g of sodium borohydride was added. Thereafter, the mixture was stirred at 10 DEG C or lower for 3 hours. 10 mL of 1 N hydrochloric acid was added to the reaction solution, and then 10 mL of water was added. The precipitate was filtered and washed with a large amount of water to obtain 0.9 g of Compound (ex-26).

0.9 g of the compound (ex-26), 2.8 g of the compound (ex-23) described in Example 5, and 0.2 g of DMAP were added to 30 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. Then, 5 mL of a dichloromethane solution of 1.3 g of DCC was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallized from methanol to obtain 1- 1-15-1) was obtained.

The phase transition temperature and NMR analysis values of the obtained compound (1-1-15-1) are as follows.

Phase transition temperature (캜): C 104 (N 79) I

_{^{1 H-NMR (CDCl 3;}} δppm): 8.10 (d, 1H), 7.91 (d, 1H), 7.71 (s, 1H), 7.53 (t, 1H), 7.44 (t, 1H), 7.24 (d, 2H), 5.81 (d, 2H), 4.87-4.77 (m, 2H), 7.18-7.11 (m, 5H), 6.83 (d, , 4.17 (t, 4H), 3.94 (t, 4H), 2.92 (t, 4H), 2.77-2.58 (m, 6H), 2.34-2.24 -1.67 (m, 12H), 1.57 - 1.42 (m, 12H).

[Example 8]

The following compound (1-1-20-1) was synthesized as follows.

[Chemical Formula 45]

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

5.5 g of the compound (ex-7), 5.8 g of the compound (ex-27) and 4.0 g of potassium carbonate were added to 55 ml of N, N-dimethylformamide (DMF) Lt; / RTI &gt; Thereto was added 1.6 g of potassium hydroxide, and the mixture was stirred at 100 占 폚 for 1 hour. Water was poured into the reaction solution, the precipitate was filtered, and washed with water and methanol. The obtained crystals were recrystallized from a mixed solution of toluene and methanol to obtain 2.4 g of the compound (ex-28).

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

1.3 g of the compound (ex-29) was added to 13 mL of ethanol, and the mixture was stirred at 10 DEG C or lower under a nitrogen atmosphere. To this, 0.3 g of sodium borohydride was added. Thereafter, the mixture was stirred at 10 DEG C or lower for 3 hours. To the reaction solution was added 13 mL of 1N hydrochloric acid water, and then 13 mL of water was added. The precipitate was filtered and washed with a large amount of water to obtain 1.3 g of Compound (ex-30).

3.7 g of the compound (ex-23), 1.3 g of the compound (ex-30) and 0.2 g of N, N-dimethyl-4-aminopyridine (DMAP) were added to 37 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere . Then, 4 mL of a dichloromethane solution containing 1.8 g of N, N'-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) and recrystallized from methanol to obtain 1- 1-20-1) was obtained.

The phase transition temperature and NMR analysis values of the obtained compound (1-1-20-1) are as follows.

Phase transition temperature (캜): C 103 I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.75 (d, 2H), 7.69-7.62 (m, 4H), 7.48 (t, 2H), 7.41-7.36 (m, 2H), 7.15-7.09 (m, 6H ), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85-4.77 (m, 4H), 2.91 (t, 4H), 2.74-2.57 1.41 (m, 12 H).

[Example 9]

The following compound (1-1-6-3) was synthesized in the same manner as in Example 8, except that 4-bromomethylbiphenyl was changed to 4-cyanobenzyl bromide.

(46)

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-3) are as follows.

Phase transition temperature (캜): C 109 I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.78 (d, 2H), 7.73 (m, 2H), 7.44 (s, 1H), 7.19-7.08 (m, 6H), 6.93 (d, 4H), 6.40 ( 4H), 3.94 (t, 4H), 2.91 (t, 4H), 4.91 (d, 2H), 6.16-6.08 (m, 2H) , 2.74-2.57 (m, 6H), 2.33-2.23 (m, 4H), 2.16-2.07 (m, 4H), 1.87-1.66 (m, 12H), 1.55-1.41 (m, 12H).

[Example 10]

The following compound (1-1-6-4) was synthesized in the same manner as in Example 8, except that 4-bromomethylbiphenyl was changed to 4-trifluoromethylbenzyl bromide.

(47)

The phase transition temperature and NMR analysis value of the obtained compound (1-1-6-4) are as follows.

Phase transition temperature (캜): C 119 (N 35) I

_{^{1 H-NMR (CDCl 3;}} δppm): 7.78 (d, 2H), 7.70 (m, 2H), 7.41 (s, 1H), 7.18-7.10 (m, 6H), 6.83 (d, 4H), 6.40 ( 4H), 3.94 (t, 4H), 2.91 (t, 4H), 4.91 (d, 2H), 6.16-6.08 (m, 2H) , 2.74-2.57 (m, 6H), 2.33-2.23 (m, 4H), 2.16-2.07 (m, 4H), 1.87-1.66 (m, 12H), 1.55-1.41 (m, 12H).

[Example 11]

The following compound (1-1-21-1) was synthesized as follows.

(48)

5.0 g of the compound (ex-3), 2.9 g of benzoyl hydrazine and 0.5 g of N, N-dimethyl-4-aminopyridine (DMAP) were added to 100 mL of dichloromethane and stirred under cooling in a nitrogen atmosphere. Then, 8 mL of a dichloromethane solution of 4.4 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC.HCl) was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. Water was added to the reaction solution, and the crystals were filtered, and the obtained crystals were washed with water and dichloromethane to obtain 5.4 g of Compound (ex-31).

5.3 g of the compound (ex-31) and 5.8 g of diisopropylethylamine (DIPEA) were added to 265 ml of acetonitrile, and the mixture was stirred at room temperature under a nitrogen atmosphere. Thereto, 11.3 g of tosyl chloride (TsCl) potassium hydroxide was added, and the mixture was further stirred at room temperature for 16 hours. The crystals were filtered, and the obtained crystals were washed with water and methanol to obtain 4.8 g of the compound (ex-32).

3.8 g of the compound (ex-32) was added to 76 mL of dichloromethane, and the mixture was stirred at -70 占 폚 or lower in a nitrogen atmosphere. Then, 6.2 g of boron tribromide was added dropwise thereto. After the dropwise addition, the mixture was stirred at -70 DEG C or lower for 2 hours, and then stirred at room temperature for 8 hours. The reaction solution was added to water, and the precipitated crystals were washed with water and methanol to obtain 3.2 g of Compound (ex-33).

5.0 g of the compound (ex-23), 1.7 g of the compound (ex-33) and 0.3 g of N, N-dimethyl-4-aminopyridine (DMAP) were added to 50 mL of dichloromethane, Respectively. Then, 5 mL of a dichloromethane solution containing 2.4 g of N, N'-dicyclohexylcarbodiimide (DCC) was added dropwise thereto. After dropwise addition, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure and the residue was purified by column chromatography (silica gel, eluant: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 10/1)) and recrystallized from methanol to obtain 1- 1-21-1) was obtained.

The phase transition temperature and NMR analysis value of the obtained compound (1-1-21-1) are as follows.

Phase transition temperature (캜): C 122 (N 99) I

_{^{1 H-NMR (CDCl 3;}} δppm): 8.17 (d, 2H), 7.90 (s, 1H), 7.63-7.55 (m, 3H), 7.30 (d, 1H), 7.21 (d, 1H), 7.13 ( 2H), 4.17 (t, 4H), 6.84 (d, 2H), 6.84 (d, 2H) , 3.94 (t, 4H), 2.91 (t, 4H), 2.74-2.57 (m, 6H), 2.33-2.25 (m, 4H), 2.16-2.08 , 1.55-1.41 (m, 12H).

&Lt; Preparation of liquid crystal composition &

[Example 12]

Using the thus synthesized compound of the present invention and the following compounds (M2-7-1), (M1-15-1), (M1-16-1) and (M1-17-1) 1 to S-12).

(49)

Table 1 shows the kind and content of the compound of the present invention in the liquid crystal composition, the kind and content of the other polymerizable liquid crystal compound, the content of the polymerization initiator, the content of the surfactant, and the content of the solvent. In Table 1,% represents the content by weight of each material when the total weight of the liquid crystal composition is 100 wt%. Irgacure 907 (BASF Japan Co., Ltd.) was used as the polymerization initiator, Phtagent FTX-218 (manufactured by Neos Corporation) as the surfactant, and the solvent was a mixed solution of cyclopentanone and toluene The mixing ratio of non-toluene was 1/1 by weight.

[Table 1]

[Example 13]

&Lt; Preparation of liquid crystal composition &

A liquid crystal composition was prepared in the same manner as in Example 12. The polymerization initiator was Adeka Cruz NCI-930 (manufactured by ADEKA Corporation), and cyclohexanone was used as the solvent.

[Table 2]

[Comparative Example 1]

The liquid crystal composition (SC) was prepared by using the above-mentioned compounds (M2-7-1), (M1-15-1) and (M1-16-1) and the following compound (C- -1 to SC-3).

(50)

[Table 3]

&Lt; Fabrication of optically anisotropic film &

[Example 14]

The liquid crystal compositions (S-1) to (S-12) prepared in Example 12 and Example 13 were applied to a glass substrate on which a rubbed alignment film was formed by spin coating. The substrate was heated at 80 DEG C for 2 minutes, cooled at room temperature for 1 minute, and the polymerizable liquid crystal layer from which the solvent had been removed was polymerized by ultraviolet light in air to obtain an optically anisotropic film in which the alignment state of the liquid crystal was fixed. These obtained optical anisotropic films were confirmed by a polarization microscope observation and a polarization analyzer, and homogeneous homogeneous orientation was observed without alignment defects.

[Comparative Example 2]

An optically anisotropic film was obtained from the liquid crystal compositions (SC-1) to (SC-3) prepared in Comparative Example 1 in the same manner as in the method described in Example 14. When these obtained optical anisotropic films were confirmed by a polarizing microscope observation and a polarization analyzer, it was confirmed that (SC-1) and (SC-2) had homogeneous homogeneous orientation without alignment defects. (SC-3) crystals precipitated, alignment defects occurred, and a film having homogeneous homogeneous orientation could not be obtained.

(SC-3) and (S-6), the film having homogeneous homogeneous orientation, which is difficult to be formed only by using the compound (C-1) Can be formed.

&Lt; Optical properties of optically anisotropic film >

[Examples 15 to 26, Comparative Examples 3 to 4]

(Re ₄₅₀ ) at a wavelength of 450 nm and a measured value (Re ₅₅₀ ) at a wavelength of 550 nm with respect to the film surface of the optically anisotropic film produced in Example 14 and Comparative Example 2, ? N at 550 nm, and wavelength dispersion characteristics are shown in Tables 4 and 5.

[Table 4]

[Table 5]

The optically anisotropic films of Examples 15 to 26 exhibited lower values of wavelength dispersion characteristics than those of Comparative Example 3. This supports the fact that the compound of the present invention is contained in the liquid crystal composition to lower the wavelength dispersion characteristics, and it has been found that the wavelength dispersion characteristics of the optically anisotropic film obtained by using the compound of the present invention can be controlled. In addition, it was confirmed that the optically anisotropic film of Example 20 had a wavelength dispersion characteristic of 1 or less and had an inverse wavelength dispersion characteristic.

&Lt; Heat resistance of optical properties of optically anisotropic film >

The retardation of the optically anisotropic film produced in Example 14 and Comparative Example 2 was measured at a wavelength of 550 nm at 90 DEG with respect to the film surface after firing at 200 DEG C for 30 minutes, and the results are shown in Tables 6 and 7. [ In Tables 6 and 7, the residual Re indicates the value of Re after the firing at 200 占 폚 for 30 minutes at an initial Re value of 100.

[Table 6]

[Table 7]

Compared with Comparative Examples 3 and 4, the optically anisotropic films of Examples 17 to 26 had a large residual ratio of retardation after baking at 200 DEG C for 30 minutes. That is, the change in optical characteristics due to heat is small.

&Lt; Mechanical properties of optically anisotropic film &

The mechanical strength of the film surface of the optically anisotropic film produced in Example 14 and Comparative Example 2 was measured by pencil hardness test, and the results are shown in Tables 8 and 7. In Tables 8 and 7, the hardness (parallel) represents the shape of the pencil lead when scratches occur in the direction parallel to the alignment direction of the optically anisotropic film, and the hardness (vertical) This indicates the hardness of the pencil lead when scratches are made in the inward direction.

[Table 8]

[Table 9]

&Lt; Preparation of liquid crystal composition &

[Example 27]

A liquid crystal composition (S-13) was prepared using the compound of the present invention and the following compounds (M2-1-1) and (M1-12-1).

(51)

These compounds were mixed at a weight ratio of compound (1-1-6-1): compound (M2-1-1): compound (M1-12-1) = 33: 33: 34. This composition is referred to as MIX1. To this MIX 1, GA-1000 (manufactured by Osaka Gas Chemical Co., Ltd.) having a weight ratio of 0.10 and Irgacure 907 (BASF Japan Co., Ltd.) with a weight ratio of 0.06 were added, and cyclohexanone was further added thereto, Of the liquid crystal composition (S-13) was 75% by weight.

&Lt; Fabrication of optically anisotropic film &

[Example 28]

The liquid crystal composition (S-13) prepared in Example 27 was applied onto a glass substrate (Matsunami Slide Glass: S-1112) by spin coating. This substrate was heated at 80 DEG C for 2 minutes, cooled at room temperature for 1 minute, and the solvent-removed coating film was polymerized under ultraviolet light in a stream of nitrogen to obtain a liquid crystal film having homogeneous homeotropic orientation.

&Lt; Optical properties of optically anisotropic film >

[Example 29]

(Re ₄₅₀ ) at a wavelength of 450 nm and a measured value (Re ₅₅₀ ) at a wavelength of 550 nm with respect to the film surface of the optically anisotropic film prepared in Example 28 at a retardation of 45 degrees in the slow axis direction The calculated wavelength dispersion characteristic was 1.0439.

The compound of the present invention has a low-wavelength dispersion property or an inverse wavelength dispersion property and shows a liquid crystal phase at a relatively low temperature. The liquid crystal composition using the compound can easily control the wavelength dispersion characteristics and is excellent in compatibility and dissolution An optically anisotropic film can be easily obtained. Further, the obtained optically anisotropic film has high mechanical strength and heat resistance. Therefore, the film containing the polymer can be used for various applications such as a retardation film, an optical compensating film, a reflective film, a selective reflective film, an antireflection film, a viewing angle compensating film, a liquid crystal alignment film, a polarizing element, a circularly polarizing element, And is preferable for a display element having such a film or element.

Claims (20)

A compound represented by the following formula (1):
[Chemical Formula 1]

(In the above formula (1)
A ¹ and A ² are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl or naphthalene-2,6-diyl , Wherein at least one of the hydrogens is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, Alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO- _{, -CF 2 O-, -OCF 2 -} , -CH 2 CH 2 -, -CF 2 CF 2 -, -OCH 2 CH 2 O-, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH _{2 COO-, -OCOCH 2 CH 2 -} , -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 - _{, -CCH 3 = N-, -N =} N- , or -C≡C-, and;
m and n are each independently an integer of 0 to 3, and 1? m + n? 4;
X ¹ is -O-, -S- or -NR ³ -, and R ³ is hydrogen, alkyl of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;
Q ¹ is hydrogen, halogen or a monovalent organic group;
R ¹ and R ² are each independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms , An alkyl ester having 1 to 20 carbon atoms, or a group represented by the following formula (2);
(2)

In the formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Y ² is a single bond or alkylene having 1 to 20 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -COO-, -OCO-, -CH = CH- or -C≡ C-; PG is a polymerizable group represented by any one of the following formulas (PG-1) to (PG-8);
(3)

In the formulas (PG-1) to (PG-8), R ⁴ is each independently hydrogen, halogen, methyl, ethyl or trifluoromethyl. The method according to claim 1,
In the above formula (1), Q ¹ is a group represented by the following formula (3) or (4)
[Chemical Formula 4]

(In the above formulas (3) and (4)
Z ³ each independently represents a single bond, -COO- or -COS-;
Z ⁴ each independently represents a single bond, -CH = CH-, -N = CH-, -CH = N-, -N = CCH ₃ -, -CCH ₃ = N-, -N = N- or -C ≡C-;
R ⁵ is hydrogen, fluorine, chlorine, cyano or alkyl having 1 to 20 carbon atoms, and -CH ₂ - in the alkyl is -O-, -S-, -CO-, -COO-, -OCO-, OCOO-, in which hydrogen may be substituted with halogen;
A ³ is independently an aromatic ring of a divalent, a 5-membered or a 6-membered ring, or a condensed ring thereof, A ⁴ is an aromatic ring of a monovalent, 5-membered or 6-membered ring, or a condensed ring thereof, and A ³ And at least one hydrogen in the aromatic ring or the condensed ring thereof in A ⁴ is fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms , An alkyl ester having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, or a thioalkyl having 1 to 5 carbon atoms;
p is an integer of 0 to 2). The method according to claim 1,
Wherein, in the formula (1), at least one of R ¹ and R ² is a group represented by the formula (2). The method according to claim 1,
In the above formula (1), X ¹ is -S-. The method according to claim 1,
In the formula (1), A ¹ and A ² each independently represent 1,4-phenylene or 1,4-cyclohexylene, wherein at least one hydrogen is fluorine, trifluoromethyl, An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyl ester having 1 to 5 carbon atoms, or an alkanoyl group having 1 to 5 carbon atoms;
Z ¹ and Z ² are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH═CHCOO-, -OCOCH═CH-, -CH ₂ CH ₂ COO- _{, -OCOCH 2 CH 2 -, -CH} 2 CH 2 OCO- or -COOCH ₂ CH ₂ - in the compounds. The method according to claim 1,
In the above formula (1), Q ¹ is a group represented by the following formula (4)
[Chemical Formula 5]

In the above formula (4), Z ³ is a single bond, -COO- or -COS-; Z ⁴ is a single bond, A ³ is each independently an aromatic ring of a divalent, five-membered or six-membered ring, or a condensed ring thereof, A ⁴ is an aromatic ring of a monovalent, And at least one hydrogen of the aromatic rings or condensed rings thereof in A ³ and A ⁴ is a condensed ring of fluorine, chlorine, cyano, nitro, trifluoromethyl, trifluoromethoxy, alkyl of 1 to 5 carbon atoms , Alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, alkanoyl of 1 to 5 carbon atoms or thioalkyl of 1 to 5 carbon atoms, and p is an integer of 0 or 1. The method according to claim 1,
In the above formula (1), at least one of A ¹ and A ² is 1,4-cyclohexylene. The method according to claim 1,
In the above formula (1), at least one of Z ¹ and Z ² is -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH ₂ -. The method according to claim 1,
In the above formula (1), R ¹ and R ² are groups represented by the following formula (2-1): Compound:
[Chemical Formula 6]

(2-1), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-, Y ² is a single bond or alkylene having 1 to 20 carbon atoms, In alkylene, at least one -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C-, and R ⁴ is hydrogen or methyl. The method according to claim 1,
In the above formula (1), Q ¹ is a group represented by any one of formulas (4-1) to (4-9)
(7)

(In the formulas (4-1) to (4-9), X ² is -O- or -S-, at least one -CH = may be substituted with -N =, and at least one hydrogen is Which may be substituted with fluorine, chlorine, cyano, trifluoroacetyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms or alkanoyl of 1 to 5 carbon atoms And * indicates the binding site). A liquid crystal composition comprising at least one compound according to claim 1. At least one of the compounds according to claim 1; And
At least one compound selected from the group of compounds represented by the following formulas (M1) and (M2)
Containing liquid crystal composition:
[Chemical Formula 8]

(In the formulas (M1) and (M2)
A ^M is each independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, fluorenone- Diyl wherein at least one of the hydrogens is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms , Alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms;
Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF _{2 O-, -OCF 2 -, -CH} 2 CH 2 -, -CF 2 CF 2 -, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -CH = CH-, -N = CH-, -CH = N-, -N = CCH 3 -, -CCH 3 = N-, -N = N- , or -C≡C-, and;
X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester;
q is an integer of 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-. At least one of the compounds according to claim 1; And
At least one of the compounds represented by the following formula (M1)
: &Lt; / RTI &gt;
[Chemical Formula 9]

(In the above formula (M1)
A ^M is independently 1,4-phenylene or 1,4-cyclohexylene, but at least one of A ^M is 1,4-cyclohexylene, wherein at least one hydrogen is fluorine, Chlorine, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkyl ester of 1 to 5 carbon atoms, or alkanoyl of 1 to 5 carbon atoms Have;
Z ^M each independently represents a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ - ;
q is an integer of 1 or 2;
X ^M is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms or alkyl of 1 to 20 carbon atoms Ester;
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-. 12. The method of claim 11,
And at least one chiral phosphorus compound. 12. The method of claim 11,
A liquid crystal composition comprising at least one dichroic dye compound. 12. A polymer obtained by irradiating ultraviolet light to the liquid crystal composition according to claim 11. The optically anisotropic film according to claim 16, wherein the polymer has optical anisotropy. 18. A polarizing plate having the optically anisotropic film according to claim 17. A display element having the optically anisotropic film according to claim 17. A display element having the polarizing plate according to claim 18.