TWI531640B - Polymerizable liquid crystal composition and optically anisotropic body - Google Patents

Description

Polymeric liquid crystal composition and optical anisotropy

The present invention relates to a polymer obtained by polymerizing a liquid crystal composition containing a polymerizable liquid crystal compound, an optically anisotropic polymer (optical anisotropic body) obtained by using the polymer, and the optically anisotropic body Liquid crystal display element.

In recent years, an optically anisotropic substance such as a polarizing plate, a polarizing reflector, or a phase difference plate utilizes a polymerizable liquid crystal compound, and is optically immobilized in a liquid crystal state to be optically anisotropic. Since the optical characteristics required for the optically anisotropic body vary depending on the purpose, a compound having a target property is required. The compound used for the optically anisotropic substance is difficult to control the aforementioned anisotropy in many cases. Therefore, it may be used in combination with various compounds to form a composition.

The present inventors have developed a polymerizable liquid crystal compound having an anthracene skeleton (Patent Documents 1 to 3). The polymerizable liquid crystal composition using these compounds can be used by adding an organic solvent to adjust the coatability thereof to prepare an ink. When a film having optical anisotropy is produced by using a polymerizable liquid crystal composition, an ink obtained by dissolving a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, or the like in an organic solvent to adjust the viscosity of the solution, homogenization, and the like is prepared. The ink is coated with the alignment-processed transparent substrate film, and the solvent is dried to align the polymerizable liquid crystal composition on the substrate film. Then, it is polymerized by ultraviolet rays to fix the alignment state. When the tilting angle stability of the polymerizable liquid crystal composition is insufficient, scattering due to alignment defects occurs, and an optically anisotropic body having a transparent appearance cannot be obtained. Further, according to the production step, when the solvent is dried and is placed at a normal temperature for a long time between polymerizations, recrystallization occurs to become a coating film appearance. The cause of the bad. Further, in the polarizing reflector using a cholesteric liquid crystal, in order to increase the brightness, a large refractive index anisotropy is required for the polymerizable liquid crystal compound of the substrate (Patent Document 4). At this time, the polymerizable liquid crystal compound of the substrate is one in which the optically active portion is not contained in the structure. When the polymerizable liquid crystal compound is uniformly aligned horizontally, various defects can be reduced. Moreover, the method of increasing the refractive index anisotropy involves introducing an unsaturated bond at a bonding site. A specific example in which an unsaturated bond is introduced to a bonding site of a polymerizable liquid crystal compound having an anthracene skeleton is disclosed in Patent Document 5, and the object thereof is to use a polymerizable compound having a triptycene skeleton, a bisphenol skeleton, and an amine system. The compound of the decane coupling agent is an essential component, and a polymerizable liquid crystal composition having a vertical alignment property and having a small control of refractive index anisotropy is provided, and the combination thereof is different from the present invention.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-238491

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-60373

[Patent Document 3] International Publication No. 2008/136265

[Patent Document 4] International Publication No. 2009/41512

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2010-163600

A first object of the present invention is to provide a polymerizable liquid crystal composition which is easy to control the tilt angle, has a wide liquid crystal phase expression region, and exhibits a liquid crystal phase to a low degree of recrystallization temperature even when left at room temperature. A second object is to provide an optically anisotropic body which is uniform in orientation and suitable for use in a polymerizable liquid crystal film. A third object is to provide a liquid crystal display element containing the optically anisotropic body.

The present inventors have found that the above-mentioned various problems can be solved by using a polymerizable liquid crystal composition containing a fluorene-based polymerizable liquid crystal compound having a cinnamate moiety as a main component, and the present invention has been completed. The polymerizable liquid crystal composition of the present invention is as shown in the following item [1].

[1] A polymerizable liquid crystal composition comprising: a component (A) selected from at least one compound of the group of compounds represented by the formula (1); and a component (B) selected from the formula (2-1). (2-2) at least one compound of the group of the compounds listed;

In the formula (1), W ^{11 is} independently hydrogen, fluorine, chlorine, methyl or ethyl; W ^{12 is} independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbon atoms or carbon number 1~ 7 alkoxy; X ^{1 is} independently hydrogen, methyl or trifluoromethyl; Y ^{1 is} independently alkyl having 1 to 20 carbon atoms, and any hydrogen in the alkyl group may be substituted by fluorine or chlorine, optionally -CH ₂ - may be substituted by -O-, -S-, -COO-, -OCO-, -OCOO-, -CH=CH- or -C≡C-;

In the formula (2-1), X ^{2A is} independently hydrogen, methyl or trifluoromethyl; W ^{21A is} independently hydrogen, fluorine, chlorine, methyl or ethyl; W ^{22A is} independently hydrogen, halogen, nitro, a cyano group or an alkyl or alkoxy group having 1 to 7 carbon atoms; n ^{2A is} independently an integer of 2 to 10; Z ^{21A is} independently a single bond, -CH ₂ CH ₂ -; in the formula (2-2), X ^{2B is} independently hydrogen, methyl or trifluoromethyl; W ^{21B is} independently hydrogen, fluorine, chlorine, methyl or ethyl; Z ^{23B is} independently a single bond, -COO-, -OCO-, -CH=CH-COO -, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CONH-, -NHCO-, -(CH ₂ ) ₄ -, -CH ₂ CH ₂ - or -C≡C-; Z ^{22B is} independently a single bond or -O-; A ^{21B is} independently 1,4-cyclohexylene, 1,4-phenylene, 1 , 3-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, the 1,3- Any hydrogen in the extended phenyl group and the 1,4-phenylene group may be fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, methyl fluorenyl, ethoxylated, ethyl fluorenyl, three fluoro-acetyl group, difluoromethyl or trifluoromethyl; Y ^2B extending independently 2 to 20 carbon atoms of alkyl group, the alkyl arbitrary extension May be substituted by fluorine or chlorine, arbitrary -CH ₂ - may be -O - or -C≡C-, CH = CH- -, - COO - , - OCO -,.

Formula (1) as a fluorene-based polymerizable liquid crystal compound having a cinnamate moiety Since the compound has good compatibility with other liquid crystal compounds and has a large refractive index anisotropy, it can be used as a constituent component of a polymerizable liquid crystal composition. The polymer of the present invention can be used, for example, as a phase difference plate, a polarizing element, a selective reflection film, a brightness enhancement film, and a viewing angle compensation film which are constituent elements of a liquid crystal display element.

The terms used in this manual are as follows. The liquid crystal compound is a general term for a compound having a liquid crystal phase and a compound which does not have a liquid crystal phase but can be used as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, and cholesterol, and in many cases, it represents a nematic phase. Polymerizability is the ability to polymerize monomers by light, heat, catalyst, etc. to provide a polymer. The compound represented by the formula (1) is sometimes referred to as the compound (1). Other compounds of the formula are also referred to by the same simplification method. The meaning of "liquid crystallinity" is not limited to having a liquid crystal phase. Even if it does not have a liquid crystal phase, the characteristics which can be used as a liquid crystal composition component when mixed with other liquid crystal compounds are also included in the meaning of liquid crystallinity. The term "arbitrary" when describing the structure of a compound means that the position is arbitrary and the number is arbitrary. Further, for example, the expression "arbitrary A may be replaced by B, C or D" includes, in addition to the case where any A is replaced by B, the case where any A is replaced by C, and the case where any A is replaced by D, A case where a plurality of As are replaced by at least two of B to D. However, the definition of any -CH ₂ - which may be substituted by -O- does not include a substitution which results in -OO-, and when any -CH ₂ - is substituted by -CH=CH- or -C≡C-, the carbon number Do not exceed the stated range. For example, Y ¹ of the formula (1) is an alkylene group having 1 to 20 carbon atoms, and any -CH ₂ - in the alkylene group may be substituted by -CH=CH- or -C≡C-, but includes -CH The carbon number of the alkyl group substituted with =CH- or -C≡C- does not exceed 20 in this case. This rule is also the same in other definitions.

When the bonding position of the substituent and the carbon atom constituting the ring is not clear, it means that the bonding position is free within the range of no chemical problem. The optically active compound having a polymerizable group of the present invention is sometimes referred to as a polymerizable optically active compound, an optically active compound, or simply a compound. The polymerizable liquid crystal composition is also sometimes referred to as a liquid crystal composition, or simply as a composition. The case where a compound has one polymerizable group is sometimes referred to as monofunctionality. Further, when the compound has a plurality of polymerizable groups, it may be referred to by a name corresponding to the number of polyfunctional or polymeric groups. The refractive index anisotropy (? n ) which is large in the present invention is a refractive index anisotropy of 0.20 or more.

The present invention includes the above item [1] and the following items [2] to [16].

[2] [1] above polymerizable liquid crystal composition according to 28, wherein the first to the formula [1] (1), W ¹¹ is independently hydrogen, methyl or ethyl; W ¹² is independently It is hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; X ^{1 is} independently hydrogen or a methyl group; and Y ^{1 is} independently an alkylene group having 1 to 12 carbon atoms. Any hydrogen in the alkyl group may be substituted by fluorine or chlorine, and any -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -OCOO-, -CH=CH- or -C≡C- In the formula (2-1) described in the item [1], X ^{2A is} independently hydrogen or methyl; W ^{21A is} independently hydrogen, methyl or ethyl; w ^{22A is} independently hydrogen, halogen, nitro, a cyano group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; n ^{2A is} independently an integer of 2 to 10; Z ^{21A is} independently a single bond, -CH ₂ CH ₂ -; In the formula (2-2) described in the above, X ^{2B is} independently hydrogen or methyl; W ^{21B is} independently hydrogen, methyl or ethyl; Z ^{23B is} independently a single bond, -COO-, -OCO-, - CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -(CH ₂ ) ₄ -, - CH ₂ CH ₂ - or -C≡C-; Z ^22B independently a single bond or -O-; A ^21B independently 1,4-cyclohexylene, 1,4- Any of hydrogen, 1,3-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, 1,3-phenylene and 1,4-phenylene It may be substituted by fluorine, chlorine, cyano, methyl, ethyl, methoxy, difluoromethyl or trifluoromethyl; Y ^{2B is} independently an alkylene group having 2 to 10 carbon atoms, and any of the alkylene groups The hydrogen may be replaced by fluorine or chlorine, and any -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-.

[3] The polymerizable liquid crystal composition according to [1], wherein, in the formula (1) described in the item [1], W ^{11 is} independently hydrogen or a methyl group; and W ^{12 is} independently hydrogen, Fluorine, chlorine, methyl or methoxy; X ^{1 is} independently hydrogen or methyl; Y ^{1 is} independently alkyl having 1 to 10 carbon atoms, and any -CH ₂ - may be -O-, -COO- , -OCO-, -OCOO-, -CH=CH- or -C≡C-substitution; in the formula (2-1) described in the item [1], X ^{2A is} independently hydrogen or methyl; W ^21A Independently hydrogen or methyl; W ^{22A is} independently hydrogen, fluorine, methyl or methoxy; n ^{2A is} independently an integer from 2 to 10; Z ^{21A is} independently a single bond, -CH ₂ CH ₂ -; In the formula (2-2) described in the above, X ^{2B is} independently hydrogen or methyl; W ^{21B is} independently hydrogen or methyl; Z ^{23B is} independently a single bond, -COO-, -OCO-, -CH=CH -COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ - or -C ≡C-; Z ^{22B is} independently a single bond or -O-; A ^{21B is} independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, 1,3-phenylene Any hydrogen in the group and 1,4-phenylene may be substituted by fluorine, methyl, methoxy or trifluoromethyl; Y ^{2B is} independently a 2 to 10 alkylene Any hydrogen in the alkyl group may be substituted by fluorine, and any -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CH=CH- or -C≡C-.

[4] The polymerizable liquid crystal composition according to any one of [1] to [3] further comprising the component (D), the component (D) being selected from the group of compounds of the formula (4) At least one compound of the group;

X ⁴ is hydrogen, methyl or trifluoromethyl; R ⁴ is cyano, -OCF ₃ , alkyl having 1 to 10 carbon atoms or alkoxy having 1 to 10 carbon atoms, and the alkyl group and alkoxy group are Any hydrogen may be substituted by fluorine; W ^{41 is} independently hydrogen, halogen, nitro, cyano or a C 1-7 alkyl or a C 1-7 alkoxy group, and any of the alkyl and alkoxy groups Can be substituted by fluorine; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond, -COO-, -OCO-, -CH=CH-COO-, - OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ - or -C≡C-; n ⁴¹ is an integer from 2 to 10; n ⁴² is an integer from 1 to 2.

[5] The polymerizable liquid crystal composition according to [4], wherein, in the formula (4) described in the item [4], X ⁴ is hydrogen or a methyl group; and R ⁴ is a cyano group, - OCF ₃ , an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; W ^{41 is} independently hydrogen, fluorine, chlorine, nitro, cyano group, alkyl group having 1 to 3 carbon atoms or carbon number 1 ~3 alkoxy, any of the alkyl and alkoxy can be substituted by fluorine; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond , -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ - or -C≡C-;n ⁴¹ is an integer from 2 to 10; n ⁴² is an integer from 1 to 2.

[6] The polymerizable liquid crystal composition according to [4], wherein, in the formula (4) described in the item [4], X ⁴ is hydrogen or a methyl group; and R ⁴ is a cyano group, - OCF ₃ , an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; W ^{41 is} independently hydrogen, fluorine, methyl or methoxy, and any hydrogen in the methyl group and the methoxy group may be Fluorine substitution; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond, -COO-, -OCO-, -CH=CH-COO-, -CH ₂ CH ₂ -COO- or -C≡C-; n ⁴¹ is an integer from 2 to 10; n ⁴² is an integer from 1 to 2.

[7] The polymerizable liquid crystal composition according to any one of [1] to [6] further comprising the component (C) which is selected from the group consisting of the compound of the formula (3) At least one compound of the group;

In the formula (3), X ^{3 is} independently hydrogen, methyl or trifluoromethyl; W ^{31 is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or C 1-7 alkoxy Any of the alkyl and alkoxy groups may be substituted by fluorine; r is an integer from 0 to 4; W ^{32 is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or carbon number 1 to 7 alkoxy group, any hydrogen in the alkyl group and alkoxy group may be substituted by fluorine; n ^{31 is} independently an integer of 2 to 10; n ³² is an integer of 1 to 3; Z ^{31 is} independently a single bond, - O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO-CH=CH-COO- or -OCOO-; Z ^{32 is} independently a single bond, -CH ₂ CH ₂ -or- CH=CH-.

[8] The polymerizable liquid crystal composition according to [7], wherein, in the formula (3) described in the item [7], X ^{3 is} independently hydrogen or a methyl group; and W ^{31 is} independently hydrogen, Fluorine, chlorine, nitro, cyano group, alkyl group having 1 to 3 carbon atoms or alkoxy group having 1 to 3 carbon atoms; any hydrogen in the alkyl group and alkoxy group may be substituted by fluorine; r is 0 to 2 An integer of W ^{32 is} independently hydrogen, halogen, nitro, cyano, C 1 to 3 alkyl or C 1 to 3 alkoxy, and any of the alkyl and alkoxy may be substituted by fluorine; n ^{31 is} independently an integer from 2 to 10; n ³² is an integer from 1 to 3; Z ^{31 is} independently a single bond, -O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO -CH=CH-COO- or -OCOO-; Z ^{32 is} independently a single bond, -CH ₂ CH ₂ - or -CH=CH-.

[9] The polymerizable liquid crystal composition according to [7], wherein, in the formula (3) described in the item [7], X ^{3 is} independently hydrogen or a methyl group; and W ^{31 is} independently hydrogen, Fluorine, cyano, methyl or methoxy, any hydrogen in the methyl and methoxy groups may be substituted by fluorine; r is an integer from 0 to 2; W ^{32 is} independently hydrogen, fluorine, cyano, methyl or A methoxy group, any hydrogen of the methyl group and the methoxy group may be substituted by fluorine; n ^{31 is} independently an integer of 2 to 10; n ³² is an integer of 1 to 3; and Z ^{31 is} independently a single bond, -O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO-CH=CH-COO- or -OCOO-; Z ^{32 is} independently a single bond, -CH ₂ CH ₂ - or -CH=CH -.

[10] The polymerizable liquid crystal composition according to any one of [1] to [9], which further comprises a nonionic surfactant.

[11] The polymerizable liquid crystal composition according to [10], wherein the nonionic surfactant is a fluorine-based, anthrone-based or hydrocarbon-based nonionic surfactant.

[12] The polymerizable liquid crystal composition according to any one of [1] to [11] wherein the component (A) is a ratio based on the total weight of the components (A) to (D). 1 to 99 wt%, component (B) is 1 to 99 wt%, component (C) is 0 to 98 wt%, and component (D) is 0 to 70 wt%.

[13] The polymerizable liquid crystal composition according to any one of [1] to [11] wherein the component (A) is a ratio based on the total weight of the components (A) to (D). 3 to 95% by weight, component (B) is 3 to 95% by weight, component (C) is 0 to 94% by weight, and component (D) is 0 to 50% by weight.

[14] The polymerizable liquid crystal composition according to any one of [1] to [11] wherein the component (A) is based on a total weight of the components (A) to (D). 5 to 90% by weight, component (B) is 5 to 90% by weight, component (C) is 0 to 90% by weight, and component (D) is 0 to 40% by weight.

[15] An optically anisotropic body obtained by polymerizing at least one of the polymerizable liquid crystal compositions according to any one of [1] to [14].

[16] A liquid crystal display element having the optically anisotropic body according to [15].

The composition of the present invention contains at least one compound selected from the group of compounds represented by the formula (1) as the component (A).

In formula (1), W ¹¹ is independently hydrogen, fluoro, chloro, methyl or ethyl, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl.

W ^{12 is} independently hydrogen, halogen, nitro, cyano, an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, preferably hydrogen, fluorine, chlorine or a C 1 to 3 alkyl group. Or a carbon number of 1 to 3 alkoxy groups, more preferably hydrogen, fluorine, chlorine, methyl or methoxy.

X ^{1 is} independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.

Y ^{1 is} independently an alkylene group having 1 to 20 carbon atoms, wherein any hydrogen may be substituted by fluorine or chlorine, and any -CH ₂ - may be -O-, -S-, -COO-, -OCO-, - OCOO-, -CH=CH- or -C≡C-substituted. Preferred are alkylene groups having 1 to 12 carbon atoms, wherein any hydrogen may be substituted by fluorine or chlorine, and any -CH ₂ - may be -O-, -COO-, -OCO-, -OCOO-, - CH=CH- or -C≡C-substituted. More preferred are alkylene groups having 1 to 10 carbon atoms, wherein any -CH ₂ - may be -O-, -COO-, -OCO-, -OCOO-, -CH=CH- or -C≡C- Replace.

The composition of the present invention contains a compound selected from the group consisting of the formulae (2-1) to (2-2) At least one compound of the group is used as the component (B).

In equation (2-1),

X ^{2A is} independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.

W ^{21A is} independently hydrogen, chlorine, chlorine, methyl or ethyl, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl.

W ^{22A is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or C 1-7 alkoxy. Preferred is hydrogen, halogen, nitro, cyano, 1-3 decyl or C 1-3 alkoxy, more preferably hydrogen, fluorine, methyl or methoxy.

n ^2A is independently an integer of from 2 to 10.

Z ^21A independently a single bond, -CH ₂ CH ₂ -.

In equation (2-2),

X ^{2B is} independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.

W ^{21B is} independently hydrogen, fluorine, chlorine, methyl or ethyl, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl.

Z ^{23B is} independently a single bond, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -,- CH ₂ O-, -OCH ₂ -, -CONH-, -NHCO-, -(CH ₂ ) ₄ -, -CH ₂ CH ₂ - or -C≡C-. Preferred are a single bond, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -,- CH ₂ O-, -OCH ₂ -, -(CH ₂ ) ₄ -, -CH ₂ CH ₂ - or -C≡C-. More preferably, a single bond, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -,- CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ - or -C≡C-.

Z ^{22B is} independently a single bond or -O-.

A ^{21B is} independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2, 6-diyl or tetrahydronaphthalene-2,6-diyl, any hydrogen of the 1,3-phenylene and 1,4-phenylene may be fluorine, chlorine, cyano, methyl, ethyl Substituent, methoxy, hydroxy, methionyl, ethoxylated, ethoxylated, trifluoroethyl, difluoromethyl, or trifluoromethyl. Preferred is 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl, the 1 Any hydrogen in the 3-phenylene group and the 1,4-phenylene group may be substituted by fluorine, chlorine, cyano, methyl, ethyl, methoxy, difluoromethyl or trifluoromethyl. More preferably, it is a 1,4-cyclohexylene group, a 1,4-phenylene group or a 1,3-phenylene group, and any hydrogen of the 1,3-phenylene group and the 1,4-phenylene group can be Fluorine, methyl, methoxy or trifluoromethyl substituted.

Y ^{2B is} independently an alkylene group having 2 to 20 carbon atoms, wherein any hydrogen may be substituted by fluorine or chlorine, and any -CH ₂ - may be -O-, -COO-, -OCO-, -CH=CH- Or -C≡C- substituted. Preferred is an alkylene group having 2 to 10 carbon atoms, wherein any hydrogen may be substituted by fluorine or chlorine, and any -CH ₂ - may be -O-, -COO-, -OCO-, -CH=CH- Or -C≡C- substituted. More preferred is an alkylene group having 2 to 10 carbon atoms, wherein any hydrogen may be substituted by fluorine, and any -CH ₂ - may be -O-, -COO-, -OCO-, -CH=CH- or - C≡C-substituted.

The composition of the present invention may further contain at least one compound selected from the group of compounds represented by the formula (4) as the component (D).

In the formula (4), X ⁴ is hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.

R ⁴ is a cyano group, -OCF ₃ , an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and any hydrogen of the alkyl group and the alkoxy group may be substituted by fluorine. Preferred are a cyano group, -OCF _3, alkyl having 1 to 10 carbon atoms or alkoxy having 1 to 10 of the.

W ^{41 is} independently hydrogen, halogen, nitro, cyano, an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, and any hydrogen of the alkyl group and the alkoxy group may be substituted by fluorine. Preferred are hydrogen, fluorine, chlorine, nitro, cyano, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and any hydrogen in the alkyl group and alkoxy group may be substituted by fluorine. . More preferably, it is hydrogen, fluorine, methyl or methoxy, and any of the methyl and methoxy groups may be substituted by fluorine.

Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-.

Z ⁴² is a single bond, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ - or -C ≡C-.

n ⁴¹ is an integer from 2 to 10.

n ⁴² is an integer from 1 to 2.

The composition of the present invention may further contain at least one compound selected from the group of compounds represented by the formula (3) as the component (C).

In the formula (3), X ^{3 is} independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.

W ^{31 is} independently hydrogen, halogen, nitro, cyano, an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, and any hydrogen of the alkyl group and the alkoxy group may be substituted by fluorine. Preferred are hydrogen, fluorine, chlorine, nitro, cyano, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and any hydrogen in the alkyl group and alkoxy group may be substituted by fluorine. . More preferably, it is hydrogen, fluorine, cyano, methyl or methoxy, and any of the methyl and methoxy groups may be substituted by fluorine.

r is an integer from 0 to 4, preferably an integer from 0 to 2.

W ^{32 is} independently hydrogen, halogen, nitro, cyano, an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, and any hydrogen in the alkyl group or alkoxy group may be substituted by fluorine. Preferred are hydrogen, a halogen, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and any hydrogen of the alkyl group and the alkoxy group may be substituted by fluorine. More preferably, it is hydrogen, fluorine, cyano, methyl or methoxy, and any of the methyl and methoxy groups may be substituted by fluorine.

n ^{31 is} independently an integer from 2 to 10.

n ^{32 is} independently an integer from 1 to 3.

Z ^{31 is} independently a single bond, -O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO-CH=CH-COO- or -OCOO-.

Z ³² is independently a single bond, -CH ₂ CH ₂ - or -CH = CH-.

The composition of the present invention may separately contain the component (C) and the component (D), These ingredients may also be contained together.

The composition of the present invention may further comprise a nonionic surfactant such as a fluorine-based, anthrone-based or hydrocarbon-based nonionic surfactant. The nonionic surfactant has an effect of improving the smoothness of the coating film.

The composition of the present invention has a liquid crystal phase having a nematic phase or a smectic phase at room temperature. When the solution in which the composition of the present invention is dissolved in a solvent is coated with a plastic substrate which has been subjected to the alignment treatment such as rubbing treatment or a support substrate whose surface is covered with a plastic film, it is formed into a horizontal alignment or a mixed alignment. Further, when a non-polymerizable or polymerizable optically active compound is added to the composition of the present invention, it becomes a torsional alignment. If a compound having a bisphenol skeleton and a monofunctional polymerizable liquid crystal compound are added to the composition of the present invention, vertical alignment is easily obtained.

The compounds used in the compositions of the present invention are illustrated below.

The compound (1) has a skeleton of a specific structure centered on an anthracene ring and two polymerizable groups. Since the compound exhibits liquid crystallinity and the polymer of the polymerizable liquid crystal compound has a three-dimensional structure, it is a harder polymer than a compound having one polymerizable group. Further, since it has a cinnamate moiety having an unsaturated bond site, it exhibits a large optical anisotropy.

The compounds (2-1) to (2-2) are compounds having two polymerizable groups centered on an anthracene ring, but the bonding sites are different from the compound (1). Since the polymer of the polymerizable compound has a three-dimensional structure, it is harder than a compound having one polymerizable group. The compound may exhibit liquid crystallinity or may not exhibit liquid crystallinity. Since this compound has a central skeleton in common with the compound (1), the melting point of the polymerizable liquid crystal composition can be lowered. Hereinafter, the compound (2) is sometimes used as a general term for the compounds (2-1) to (2-2) or compounds derived from the compounds.

The compound (4) has a phenylene skeleton and a polymerizable group, and the inclination angle of the other liquid crystal molecules can be increased or the melting point can be lowered. The compound derived from the compound (4) hereinafter is sometimes collectively referred to as the compound (4), as in the case of the compound (2).

The compound (3) has a phenylene skeleton and two polymerizable groups, and is coated with a rubbing-treated substrate having an alignment film polymer having no side chain or a nonionic interface activity depending on conditions such as a supporting substrate and an additive. When the liquid crystal composition is added to the liquid, it is easy to horizontally align. Moreover, there is also a tendency to exhibit a liquid crystal phase in a wide temperature range. The compound derived from the compound (3) hereinafter is sometimes collectively referred to as the compound (3) as in the case of the above compound (2).

The composition of the present invention may contain other polymerizable compounds different from the compounds (1), (2-1) to (2-2), (3), (4) and the nonionic surfactant. In order to improve the adhesion between the coating film and the support substrate, a decane coupling agent may also be contained. Additives such as a polymerization initiator, a photosensitizer, and the like which are suitable for the polymerization reaction may also be contained. In order to improve the properties of the polymer, the composition may also contain additives such as an ultraviolet absorber, an antioxidant, a radical scavenger, a light stabilizer, and a chain transfer agent. An organic solvent may also be included to form a coating film of uniform thickness.

The ratio of each component in the composition of the present invention is explained below.

The preferred ratio of the component (A) is from 1 to 99% by weight, more preferably from 3 to 95% by weight, still more preferably from 5 to 90% by weight, based on the total weight of the components (A) to (D).

The preferred ratio of the component (B) is from 1 to 99% by weight, more preferably from 3 to 95% by weight, still more preferably from 5 to 90% by weight, based on the total weight of the components (A) to (D).

The preferred ratio of the component (D) is 0 to 70% by weight, more preferably 0 to 50% by weight, still more preferably 0 to 40% by weight based on the total weight of the components (A) to (D).

The preferred ratio of the component (C) is based on the total weight of the components (A) to (D). The time is 0 to 98% by weight, more preferably 0 to 94% by weight, and still more preferably 0 to 90% by weight.

A preferred ratio when a nonionic surfactant is added is 0.0001 to 0.03 by weight based on the total weight of the components (A) to (D).

The preferred ratio when the decane coupling agent is added is 0.01 to 0.15, more preferably 0.03 to 0.10 by weight based on the total weight of the components (A) to (D).

When a further polymerizable compound is added, the preferred ratio is 0.01 to 0.50, preferably 0.03 to 0.30 by weight based on the total weight of the components (A) to (D). When an additive such as a polymerization initiator is used, the amount can be the minimum amount which can be achieved.

The combination of the components in the composition of the present invention is explained below.

In the case of forming a horizontal alignment, it is preferred that the combination of the component (A), the component (B) and the component (C), the component (A), the component (B) and the component (D), and the component (A) ), a combination of component (B), component (C), and component (D).

When adjusting the alignment or coating uniformity, it can also be combined with a nonionic surfactant. When the adhesion to the support substrate is improved, it may be combined with a decane coupling agent. Further, other polymerizable compounds may be further combined in each combination.

Next, the synthesis method of the compound will be explained. The compounds used in the present invention can be obtained by Methoden der Organischen Chemie (Houben Weyl, published by Georg Thieme Verlag, Stuttgart), Organic Reactions (published by John Wily & Sons Inc.), Organic Syntheses (published by John Wily & Sons Inc.), Comprehensive The organic synthesis method described in Organic Synthesis, published by Pergamon Press, New Experimental Chemistry Lecture (Maruzen Publishing), and the like are combined and synthesized.

The synthesis of the compound (1) can be found in the specification of U.S. Patent No. 5,770,107.

The synthesis method of the compound (2-1) to (2-2) is described in the specification of JP-A-2003-238491, JP-A-2006-307150, and International Publication No. 2008/136265.

The compound (4) can be synthesized by the method described in Macromolecules, 26, 6132-6134 (1993), German Patent No. 19504224, and International Publication No. 1997/00600.

The synthesis method of the compound (3) is described in Makromol. Chem., 190, 3201-3215 (1989), Makromol. Chem., 190, 2255-2268 (1989), International Publication No. 97/00600, and US Pat. No. 5770107. Japanese Patent Laid-Open No. 2004-231638 and the like are described.

The component compounds are exemplified below. Preferred examples of the compound (1) are shown below.

In the formulae (1-1) to (1-6), X ^{1 is} independently hydrogen, chlorine, methyl or trifluoromethyl, and n is independently an integer of 2 to 20.

Preferred examples of the compound (2-1) are shown below.

In the formulae (2-1-A) to (2-1-D), X ^{2A is} independently hydrogen, methyl or trifluoromethyl, and n ^{2A is} independently an integer of 2 to 10.

Preferred examples of the compound (2-2) are shown below.

In the formulae (2-2-1) to (2-2-36), X ^{2B is} independently hydrogen, methyl or trifluoromethyl, and n ^{2B is} independently an integer of from 2 to 15.

Preferred examples of the compound (4) are shown below.

In the formulae (4-1) to (4-13), X ^{4 is} independently hydrogen or methyl, W ^{41 is} independently hydrogen or fluorine, and R ⁴ is an alkyl group having 1 to 7 carbon atoms and a carbon number of 1 to 7. Alkoxy or -OCF ₃ , n ⁴¹ is an integer from 2 to 10.

Preferred examples of the compound (3) are shown below.

In the formula (3-1) ~ (3-11), X 3 are independently hydrogen, methyl or trifluoromethyl, W ³² is independently hydrogen or fluorine, n ³¹ represents an integer of from 2 to 10.

Specific examples of the compounds (1) and (2-1) to (2-2), (4) and (3) are shown below.

Next, a nonionic surfactant is exemplified.

An example of an anthrone-based nonionic surfactant is Polyflow ATF-2, Glanol 100, Glanol 115, Glanol 400, Glanol 410, Glanol manufactured by Kyoeisha Chemical Co., Ltd., which is based on unmodified or modified anthrone. 435, Glanol 440, Glanol 450, Glanol B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302, BYK-306, BYK-307, BYK -310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344 , BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK-3510 and BYK-3570.

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

Examples of the hydrocarbon-based nonionic surfactant are Polyflow No. 3, Polyflow No. 50 EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85 HF, which are mainly composed of an acrylic polymer. Polyflow No.90, Polyflow No.95, Polyflow No.99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392 And BYK-Silclean 3700.

In addition, the above Polyflow and Glanol are the names of products sold by Kyoeisha Chemical Co., Ltd. BYK is the name of the product sold by BYK-CHEMIE JAPAN. Ftergent, FTX and KB are the names of the products sold by Neos.

These surfactants may be used singly or in combination of two or more.

Next, another polymerizable compound, an additive, and an organic solvent are exemplified. These compounds may also be commercially available. Examples of the other polymerizable compound are a compound having one polymerizable group, a compound having two polymerizable groups, and a polyfunctional compound having three or more polymerizable groups.

Examples of the compound having one polymerizable group are styrene, ring-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinylpyrrolidone, vinyl sulfonic acid, fatty acid ethylene. Esters (such as vinyl acetate), α , β -ethylenically unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl (meth)acrylates ( Alkyl carbon number 1~18), hydroxyalkyl (meth) acrylate (hydroxyl carbon number 1~18), amino acid alkyl (meth) acrylate (amine alkyl carbon number 1~18) An ether oxyalkyl ester of (meth)acrylic acid (containing an etheroxyalkyl group having 3 to 18 carbon atoms, such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methyl carvness, Ethyl celery and butyl celery, N-vinyl acetamide, p-tert-butyl butyl benzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, Vinyl pivalate, vinyl 2,2-dimethylbutyrate, vinyl 2,2-dimethylvalerate, vinyl 2-methyl-2-butyrate, vinyl propionate, stearic acid Vinyl ester, vinyl 2-ethyl-2-methylbutyrate, (meth)acrylic acid Pentyloxyethyl ester, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethantane (meth)acrylate Base ester, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-propenyl methoxyethyl succinic acid, 2-propenyl ethoxyethyl hexahydro phthalate Formic acid, 2-propenyloxyethyl phthalic acid, 2-propenyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloxyethyl phosphate, 2-methyl phosphate a mono- or di-(meth) acrylate of a polyalkylene glycol such as a propylene methoxyethyl ester, a polyethylene glycol having a polymerization degree of from 1 to 100, a polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, or Mono(meth)acrylic acid of polyalkylene glycol, such as polyethylene glycol, polypropylene glycol, and copolymer of ethylene oxide and propylene oxide, which are terminated with a carbon number of 1 to 6 alkyl groups and having a polymerization degree of 1 to 100 ester.

Examples of the compound having two polymerizable groups are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate. Ester, dimethylol tricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A ethylene oxide Addition of diacrylate, bisphenol A glycidyl diacrylate (Viscoat V#700), polyethylene glycol diacrylate, and methacrylate compounds of these compounds, formula (α-1)~(α- 6) A polymerized bisphenol hydrazine derivative having a phenolphthalein structure as shown. These compounds are suitable for further increasing the degree of hardening of the polymer.

Examples of the compound having three or more polymerizable groups are pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethyloloxirane addition tris(meth)acrylic acid. Ester, tris(meth)acryloxyethyl phosphate, tris((meth)propenyloxyethyl)isocyanate, alkyl modified dipentaerythritol tri(meth)acrylate, Ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl modification Dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl modification Dipentaerythritol penta (meth) acrylate, Viscoat V#802 (functional number = 8), Viscoat V #1000 (number of functional groups = average 14). "Viscoat" is the trade name of Osaka Organic Chemical Company. The compound having a functional group number of 16 or more may be Boltorn H20 (16-functional), Boltorn H30 (32-functional), sold by Perstorp Specialty Chemicals, Boltorn H40 (64-functional) is obtained by acrylation of a raw material.

In order to optimize the polymerization rate of the polymerizable liquid crystal composition, a known photoradical polymerization initiator may be used, and the amount thereof is preferably 0.0001 by weight based on the total weight of the components (A) to (D). ~0.20, 0.001~0.15 is better, and 0.01~0.15 is better. An example of a photoradical polymerization initiator is 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy group. -1,2-diphenylethane-1-one (Irgacure 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone) ), Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Darocur 4265, Darocur MBF, Darocur TPO, Irgacure 784, Irgacure 754, Irgacure OXE01 and Irgacure OXE02. The above-mentioned Darocur and Irgacure are the names of products sold by BASF Japan. A known sensitizer (isopropyl thioxanthone, diethyl thioxanthone, ethyl 4-dimethylaminobenzoate (Darocur EDB), 4-dimethylamino group may also be added thereto. 2-ethylhexyl benzoate (Darocur EHA), etc.).

The photoradical polymerization initiator may also be used as described below.

P-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenyl acridine, 9,10-benzoxazine, benzophenone/Michler's ketone mixture, hexaaryldiimidazole/mercaptobenzimidazole mixture, 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one, benzoin dimethyl ketal, 2-methyl-1-[4-(methylthio)benzene a mixture of 2-morpholinopropan-1-one, 2,4-diethyloxaxanone/p-dimethylaminobenzoic acid methyl ester, benzophenone/methyltriethanolamine.

The mechanical properties of the polymer can be controlled by adding one or more chain transfer agents to the polymerizable liquid crystal composition. The length of the polymer chain or the length of the two crosslinked polymer chains in the polymer film can be controlled by using a chain transfer agent, and the length of both can be controlled at the same time. As the amount of chain transfer agent increases, the polymer chain length decreases. A preferred chain transfer agent is a thiol compound. Examples of monofunctional thiols are dodecyl mercaptan, 2-ethylhexyl-(3-mercaptopropionic acid) ester. Polyfunctional thiols such as trimethylolpropane tris(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, 1,4-bis(3-mercaptobutyloxy)butane (Karenz MT) BD1), pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz MT PE1) and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4, 6(1H,3H,5H)-trione (Karenz MT NR1). "Karenz" is the trade name of Showa Denko.

In order to prevent polymerization from occurring upon storage, a polymerization inhibitor may be added to the polymerizable liquid crystal composition, and a known one may be used. Preferred examples are 2,5-di(tributyl)hydroxytoluene (BHT) and p-benzene. Diphenol, methyl blue, diphenylpicrylhydrazide (DPPH), benzothiazine, 4-nitrosodimethylaniline (NIDI), o-hydroxybenzophenone.

In order to improve the preservability of the polymerizable liquid crystal composition, a polymerization inhibitor may be added to promote polymerization of the polymerizable compound when a radical is generated in the composition or the composition solution. A phenolic antioxidant, a sulfur-based antioxidant, and a phosphate-based antioxidant can be used as a polymerization inhibitor.

In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant, or the like may be added. Examples of UV absorbers are 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, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Adekastab LA-31, Adekastab 1413, and Adekastab LA-51. "Tinuvin" is the trade name of BASF Japan, and "Adekastab" is the trade name of Solectron.

Examples of light stabilizers are Tinuvin 111 FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Chimassorb 119FL, Chimassorb 944FL, Chimassorb 944LD, Adekastab LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63P, Adekastab LA-68LD, Adekastab LA-77, Adekastab LA-82, Adekastab LA-87 Cyasorb UV-3346 manufactured by Cytec and Good-rite UV-3034 by Goodrich. "Chimassorb" is the trade name of BASF Japan.

Antioxidants such as Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by Asahi Chemical Co., Ltd., Sumilizer BHT, Sumilizer BBM-S and Sumilizer GA-80 sold by Sumitomo Chemical Co., Ltd. And Irganox 1076, Irganox 1010, Irganox 3114 and Irganox 245 sold by BASF Japan. Commercial products of these can also be used.

In order to control the adhesion to the substrate, it is also possible to form a polymerizable liquid crystal composition. Further, a decane coupling agent is added. Specifically, vinyl trialkoxy decane, 3-isocyanate propyl triethoxy decane, N-(2-aminoethyl)-3-aminopropyl trialkoxy decane, N-(1 ,3-dimethylbutylidene)-3-(trialkoxyindenyl)-1-propylamine, 3-glycidoxypropyltrialkoxydecane, 3-chlorotrialkoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrialkoxydecane, and the like. Other examples are dialkoxymethyl decane in which one of the alkoxy groups (three) in the compounds is substituted with a methyl group.

The polymerizable liquid crystal composition may be directly coated on the substrate surface. However, in general, in order to facilitate coating, a polymerizable liquid crystal composition is diluted with a solvent, or each component of the polymerizable liquid crystal composition is dissolved in a solvent to prepare a polymerizable liquid crystal composition solution containing a polymerizable liquid crystal composition and a solvent, and This solution was applied. These solvents may be used singly or in combination of two or more. Examples of the solvent are an ester solvent, a guanamine solvent, an alcohol solvent, an ether solvent, a glycol monoalkyl ether solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a halogenation. An aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone solvent, and an acetate solvent.

Preferred examples of the ester solvent are alkyl acetates (e.g., methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, Amyl acetate and isoamyl acetate), ethyl trifluoroacetate, alkyl propionate (eg methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and propionic acid) Butyl ester), alkyl butyrate (such as methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), dialkyl malonate (such as malonic acid) Diethyl ester), alkyl glycolate (such as methyl glycolate and ethyl glycolate), alkyl lactate (such as methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate) And ethylhexyl lactate), monoacetin, γ -butyrolactone and γ -valerolactone.

Preferred examples of the guanamine-based solvent are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N-methylpropionamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylacetamide dimethyl acetal, N-methyl caprolactam and dimethyl Imidazolinone.

Preferred examples of the alcohol solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, tertiary butanol, secondary butanol, butanol, 2-ethyl Butanol, n-hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-pentanol, hexafluoro-2-propanol, Glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, 1,3-butanediol, 1,4-butanediol , 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and Methylcyclohexanol.

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

Preferred examples of the diol monoalkyl ether solvent are ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ethers (e.g., diethylene glycol). Alcohol monoethyl ether), triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (such as dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether Acid esters (such as ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether acetate (such as diethylene glycol monoethyl ether acetate), triethylene glycol monoalkyl ether acetate Propylene glycol monoalkyl ether acetate (example) Such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (such as dipropylene glycol monomethyl ether acetate), and diethyl Alcohol methyl ethyl ether.

Preferred examples of the aromatic hydrocarbon solvent are benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, cumene, n-propylbenzene, tert-butylbenzene, and secondary butyl. Benzene, n-butylbenzene, and tetralin. A preferred example of the halogenated aromatic hydrocarbon solvent is chlorobenzene. Preferred examples of the aliphatic hydrocarbon solvent are hexane and heptane. Preferred examples of the halogenated aliphatic hydrocarbon solvent are chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene and tetrachloroethylene. Preferred examples of the alicyclic hydrocarbon-based solvent are cyclohexane and decalin.

Preferred examples of the ketone solvent are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

Preferred examples of the acetate-based solvent are ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetonitrile acetate, and acetic acid-1-methoxy- 2-propyl ester.

From the viewpoint of the solubility of the polymerizable liquid crystal compound, a guanamine solvent, an aromatic hydrocarbon or a ketone solvent is preferably used. When considering the boiling point of the solvent, it is preferred to use an ester solvent, an alcohol solvent or an ether solvent in combination. A diol monoalkyl ether solvent. The choice of the solvent is not particularly limited. However, when a plastic substrate is used as the support substrate, in order to prevent deformation of the substrate, the drying temperature must be lowered and the solvent is not eroded. The solvent to be preferably used at this time is an aromatic hydrocarbon solvent, a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, an acetate solvent, or a glycol monoalkyl ether solvent.

The ratio of the solvent in the polymerizable liquid crystal composition solution is the total weight of the solution The benchmark is 50% to 95%. The lower limit of the range is a value considering the solubility of the polymerizable liquid crystal compound and the optimum viscosity when the solution is applied, and the upper limit is a value in consideration of the cost of the solvent and the economical time of the solvent or the thermal energy. The preferred range of the ratio is 60% to 90%, and 70% to 85% is more preferable.

In the following description, a polymer (optical anisotropic body) obtained by polymerizing a polymerizable liquid crystal composition is often referred to as a liquid crystal film. The liquid crystal film can be obtained in the following manner. First, the polymerizable liquid crystal composition solution is applied onto a support substrate and dried to form a coating film. The coating film is irradiated to polymerize the polymerizable liquid crystal composition, and the composition in the coating film is fixed in a nematic alignment in a liquid crystal state. The support substrates that can be used are glass and plastic films. Examples of plastic films are polyimine, polyamidimide, polyamine, polyether phthalimide, polyether ether ketone, polyether ketone, polyketone sulfide, polyether oxime, polyfluorene, polyphenylene Thioether, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyethylene A film of an alcohol, a polypropylene, a cellulose, a cellulose triester and a partial saponified product thereof, an epoxy resin, a phenol resin, and a cycloolefin resin.

The cycloolefin-based resin may, for example, be a norbornene-based resin or a dicyclopentadiene-based resin, but is not limited thereto. Among these resins, those which are hydrogenated without an unsaturated bond or an unsaturated bond, for example, a hydrogenated product of one or two or more kinds of norbornene-based monomers, one or two kinds of ring-opening (co)polymers, are suitable. Addition (co)polymer of norbornene-based monomer, addition copolymer of norbornene-based monomer and olefin-based monomer (ethylene, α-olefin, etc.), norbornene-based monomer and ring An addition copolymer of an olefinic monomer (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and the like, and the like, specifically ZEONEX, ZEONOR (manufactured by Japan ZEON Co., Ltd.), ARTON (manufactured by JSR Corporation), TOPAS (manufactured by Ticona Co., Ltd.), APEL (manufactured by Mitsui Chemicals, Inc.), S-SINA (manufactured by Sekisui Chemical Co., Ltd.), and OPTOREZ (manufactured by Hitachi Chemical Co., Ltd.) .

The plastic film may be a uniaxially stretched film, or may be a biaxially stretched film, and may be subjected to a surface treatment such as hydrophilization treatment or hydrophobization treatment such as corona treatment or plasma treatment. The hydrophilization treatment method is not particularly limited, and is preferably corona treatment or plasma treatment, and particularly preferably plasma treatment. The plasma treatment can be carried out by the methods described in JP-A-2002-226616, 2002-121648, and the like. Moreover, in order to improve the adhesion between the liquid crystal film and the plastic film, a tackifying coating layer may also be formed. As long as the adhesion-promoting coating can improve the adhesion between the liquid crystal film and the plastic film, there is no problem in any inorganic or organic material. Moreover, the plastic film may also be a laminated film. Instead of the plastic film, a metal substrate such as aluminum, iron or copper having a slit-like groove on the surface thereof or a glass substrate such as an alkali glass, a borax glass or a vermiculite glass which is etched into a slit shape may be used.

On the support substrate such as the glass or plastic film, when a liquid crystal film which is horizontally aligned and mixed and aligned is formed before the formation of the polymerizable liquid crystal composition coating film, physical and mechanical surface treatment by friction or the like is performed. When the vertical alignment liquid crystal film is formed, surface treatment such as rubbing is often not performed, but it is also possible to prevent alignment defects and the like. The rubbing treatment may be carried out by any method, but generally, an alignment cloth containing materials such as enamel, cotton, and 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 or moving the support substrate in a state where the roller is fixed. The support substrate can be directly rubbed, or the polymerization can be pre-set on the support substrate. The film is covered and rubbed. The method of rubbing treatment is as described above. Depending on the type of the supporting substrate, the yttrium oxide may be vapor-deposited on the surface thereof to impart an alignment ability.

In the case of coating a polymerizable liquid crystal composition or a solution thereof, examples of a coating method capable of obtaining a uniform film thickness are a spin coating method, a micro gravure coating method, a gravure coating method, a wire bar coating method, and a dip coating method. Spraying method, meniscus coating method and die coating method. In particular, when the surface treatment of the substrate is not performed by friction or the like to control the alignment of the liquid crystal composition, a wire bar coating method or the like for applying a shear stress to the liquid crystal composition at the time of coating may be used.

When a solution of the polymerizable liquid crystal composition of the present invention is applied, the solvent is removed after coating, and a polymerizable liquid crystal layer having a uniform thickness is formed on the support substrate, that is, a film layer of a polymerizable liquid crystal composition. The solvent removal conditions are not particularly limited as long as the solvent can be removed substantially and dried until the polymerizable liquid crystal composition coating film has no fluidity. The solvent can be removed by air drying at room temperature, drying with a hot plate, drying in a drying oven, blowing warm air or hot air. The type and composition ratio of the compound used in the polymerizable liquid crystal composition may be completed by aligning the nematic alignment of the polymerizable liquid crystal composition during drying of the coating film. Therefore, the coating film of the drying step can be supplied to the polymerization step without going through the heat treatment step described later.

The type and composition ratio of the compound used for the polymerizable liquid crystal composition, the presence or absence of the addition of the photopolymerization initiator, or the addition amount thereof, the temperature and time when the coating film is heat-treated, the wavelength of light used for illumination, and the light source. The preferred range of the amount of light to be irradiated or the like is different. Therefore, the temperature and time of the heat treatment of the coating film described below, the wavelength of the light used for illuminating, and the condition of the amount of light irradiated from the light source always show a rough range.

The heat treatment of the coating film is preferably performed by removing the solvent to obtain uniformity of the polymerizable liquid crystal. Performed under aligning conditions. It can also be carried out at a liquid crystal transformation point or higher of the polymerizable liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated to a temperature at which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase, and the polymerizable liquid crystal composition in the coating film is formed in a nematic alignment. In the temperature range in which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase, the coating film temperature may be changed to form a nematic alignment. This method is a method in which the coating film is heated to a high temperature range in the above temperature range to substantially complete the nematic alignment in the coating film, and then the temperature is lowered to further order alignment. When any of the above heat treatment methods is employed, the heat treatment temperature is room temperature to 120 ° C, room temperature to 100 ° C is preferred, room temperature to 90 ° C is better, and room temperature to 85 ° C is more preferable. The heat treatment time is 5 seconds to 2 hours, preferably 10 seconds to 40 minutes, and more preferably 20 seconds to 20 minutes. In order to raise the temperature of the film layer containing the polymerizable liquid crystal composition to a predetermined value, the heat treatment time is preferably 5 seconds or longer. In order not to lower the productivity, it is preferred to set the heat treatment time to within 2 hours. The polymerizable liquid crystal layer of the present invention can be obtained in this manner.

The nematic alignment state of the polymerizable liquid crystal compound formed in the polymerizable liquid crystal layer can be immobilized by polymerizing the polymerizable liquid crystal compound by irradiation. The wavelength of light used for illuminating is not particularly limited, and an electron beam, an ultraviolet ray, a visible ray, an infrared ray (heat ray), or the like can be used, and ultraviolet light or visible light is usually used. The wavelength range is 150 to 500 nm, and 250 to 450 nm is preferable. 300~400nm is better. Examples of the light source are low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lamps), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short-arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, mercury xenon lamps). Preferred examples of the light source are metal halide lamps or xenon lamps, ultrahigh pressure mercury lamps, and high pressure mercury lamps. A filter or the like may be provided between the light source and the polymerizable liquid crystal layer to pass only a specific wavelength region to select a wavelength region of the illumination source. The amount of light irradiated from the light source is 2 to 5000 mJ/cm ² when it reaches the coating film surface, preferably 10 to 3000 mJ/cm ^{2 , more} preferably 100 to 2000 mJ/cm ² . The temperature condition at the time of illumination is preferably set in the same manner as the above heat treatment temperature. Further, the environment of the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere, and an air environment, and a nitrogen atmosphere or an inert gas atmosphere is preferred from the viewpoint of improving hardenability.

When the polymerizable liquid crystal layer of the present invention and a liquid crystal film obtained by polymerizing it by light or heat are used in various optical elements, or when used as an optical compensation element used in a liquid crystal display device, the tilt of the thickness direction is controlled. The angular distribution is very important.

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

The horizontal alignment is that the tilt angle is uniformly close to 0 degrees from the substrate interface to the free interface, especially between 0 and 5 degrees. The alignment state can be The polymerizable liquid crystal composition of the present invention containing the components (A) and (B) and a nonionic surfactant as a component is applied onto a surface of a support substrate subjected to surface treatment such as rubbing to form a coating film.

The weight percentage (wt%) of the components (A) to (D) in the following table is based on the total weight of the components (A) to (D). In the present invention, in order to obtain a uniform horizontal alignment, it is preferred that the component (A) is used in a proportion of from 1 to 99% by weight, more preferably from 3 to 95% by weight, even more preferably from 5 to 90% by weight. Preferred examples of the compound (1) are the compounds (1-1-1) to (1-2-6). The compounds of the compound (1) can also be used in various combinations.

The use ratio of the component (B) is preferably from 1 to 99% by weight, more preferably from 3 to 95% by weight, still more preferably from 5 to 90% by weight. Preferred examples of the compound (2) are the compounds (2-1-A1) to (2-1-D5), (2-2-1-1) to (2-2-10-2), and (2-2). -13-1)~(2-2-36-1). Further, a plurality of compounds represented by the compound (2) may be used in combination.

The component (D) is not necessarily used, and the use ratio when used for the adjustment of the melting point or the like is 1 to 70% by weight, preferably 1 to 50% by weight, more preferably 1 to 40% by weight. Preferred examples of the compound (4) are the compounds (4-1-1) to (4-13-2). Further, various compounds of the compound (4) may be used in combination.

Although the component (C) can be used for optical anisotropy adjustment or the like, it is not necessarily used. A preferred ratio when using the component (C) is 1 to 98% by weight, more preferably 1 to 94% by weight, still more preferably 1 to 90% by weight.

Preferred examples of the compound (3) are the compounds (3-4-1) to (3-4-6), (3-5-1) to (3-5-6), (3-6-1)~ (3-11-4). Further, various compounds of the compound (3) may be used in combination.

The ratio of use of the nonionic surfactant is in the range of 0.0001 to 0.03 by weight based on the total weight of the components (A) to (D). Nonionic boundary Surfactants can also be used in various combinations.

When it is difficult to form a uniform horizontal alignment, the oblique alignment property is considered to be strong, so that the component (C) is incremented, the component (D) is minimized, or the nonionic surfactant is increased, and the like. A uniform horizontal alignment is obtained.

The liquid crystal compound having no polymerizable group may be contained in the composition of the present invention, and an example thereof is described in LiqCryst (LCI Publisher GmbH, Hamburg, Germany) of a liquid crystal compound. Specific examples of the liquid crystal compound having no polymerizable group are described on pages 66 to 69 of JP-A-2011-148762. The polymerizable liquid crystal composition of the present invention has good compatibility with other liquid crystal compounds, and may further contain an additive such as a dichroic dye or a fluorescent dye. When the polymerizable liquid crystal composition is polymerized, a composite material having a liquid crystal compound having no polymerizable group can be obtained.

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

Specific examples are the compounds described in paragraph 0170 on page 70, paragraph 0159 to page 81 of JP-A-2011-148762.

A polymerizable liquid crystal composition containing an appropriate amount of an optically active compound or a polymerizable liquid crystal composition containing an appropriate amount of an optically active polymerizable compound is applied onto an oriented substrate to carry out polymerization to obtain a helical structure. (torsion structure) retardation film. The helical structure is fixed by polymerization of a polymerizable liquid crystal composition. The properties of the resulting liquid crystal film depend on the helical pitch of the resulting helical structure. The length of the spacer can be adjusted by the type and amount of the optically active compound. The optically active compound added may be one type but offset A variety of temperatures can be used depending on the temperature dependence of the spiral pitch. Further, the polymerizable liquid crystal composition may contain other polymerizable compounds in addition to the optically active compound.

The selective reflection of visible light, which is a characteristic of the liquid crystal film, is a spiral structure that acts on incident light and reflects circularly polarized or elliptically polarized light. The selective reflection characteristic is expressed by λ = n ‧Pitch ( λ is the center wavelength of the selective reflection, n is the average refractive index, and Pitch is the spiral pitch), so changing the n or Pitch can appropriately adjust the center wavelength ( λ ) and the wavelength interval (△) λ ). In order to improve the color purity, the wavelength interval (Δ λ ) may be reduced, and when it is desired to reflect the broadband band, the wavelength interval (Δ λ ) may be increased. In addition, the selective reflection is also greatly affected by the thickness of the polymer. In order to maintain color purity, the thickness must not be too small. In order to maintain uniform orientation, the thickness must not be too large. Therefore, it is necessary to adjust a moderate thickness, preferably 0.5 to 25 μm, more preferably 1 to 10 μm.

By making the helical pitch shorter than the wavelength of visible light, a negative C plate as described by WHde Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. In order to shorten the spiral pitch, an optically active compound having a large helical twisting force (HTP) can be used and the amount of addition thereof can be increased. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less, which is an optical compensation film suitable for liquid crystal display elements such as VAN, VAC, and OCB type.

The liquid crystal film can be used in a reflection film in which a reflection wavelength region is set to a near-infrared region (wavelength of 800 to 2,500 nm) as described in Japanese Laid-Open Patent Publication No. 2004-333671, by making the spiral pitch larger than the visible light wavelength. In order to lengthen the spiral pitch, an optically active compound having a small helical twisting force or a reducing amount of the optically active compound may be used.

The optically active compound may be appropriately mixed with a polymerizable liquid crystal composition as a substrate as long as it can induce a helical structure, and any optically active compound can be used. Further, the polymerizable compound may be any of the non-polymerizable compounds, and an optimum compound may be added as needed. When heat resistance and solvent resistance are considered, a polymerizable compound is preferable.

Further, among the above-mentioned optically active compounds, those having a large helical twisting force (HTP) are preferred in terms of shortening the helical pitch, and a representative example of such a compound is disclosed in GB 2298202 and DE 10221751.

The thickness (film thickness) of the liquid crystal film is not the same as the thickness corresponding to the target element or the birefringence (optical anisotropy value) of the liquid crystal film. Therefore, the range of thickness is not the same in each target, and the standard is 0.05 to 100 μm, preferably 0.1 to 50 μm, and more preferably 0.5 to 20 μm. The haze value of the liquid crystal film is preferably 1.5% or less, and the transmittance is preferably 80% or more. The haze value is preferably 1.0% or less, and the penetration rate is more preferably 95% or more. Regarding the transmittance, it is preferable to satisfy the conditions in the visible light region.

The liquid crystal film can be effectively used as an optical compensation element suitable for liquid crystal display elements (especially active matrix type and passive matrix type). Examples of liquid crystal display element types suitable for the liquid crystal film as an optical compensation film are a transverse electric field switching (IPS) type, an optical compensation birefringence (OCB) type, a twisted nematic (TN) type, and a super twisted nematic (STN) type. , electronically controlled birefringence (ECB) type, vertical alignment phase distortion (DAP) type, color super vertical surface (CSH) type, vertical alignment nematic / cholesterol (VAN / VAC) type, optical mode interference (OMI) type, Super birefringence effect (SBE) type, etc. Further, the liquid crystal film may be used as a phase retarder for a display element such as a guest type, a ferroelectric type or an antiferroelectric type. Further, the optimum value of the parameter such as the distribution or the thickness in the thickness direction of the tilt angle required for the liquid crystal film is significantly determined depending on the type of the liquid crystal display element to be compensated for and the optical parameters thereof, and therefore varies depending on the type of the element.

The liquid crystal film can also be used as an optical element integrated with a polarizing plate or the like, and is disposed outside the liquid crystal cell at this time. On the other hand, the liquid crystal film as the optical compensation element can be disposed inside the liquid crystal cell because no impurity is eluted or eluted to the liquid crystal filled in the cell. For example, by applying the method disclosed in Japanese Laid-Open Patent Publication No. 2008-01943, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter. A horizontal alignment liquid crystal film formed by combining with a dichroic dye can also be used as an absorption type polarizing plate. Further, a horizontal alignment liquid crystal film which is composited with a fluorescent dye can also be used as a polarized light-emitting film.

[Example]

The invention is illustrated in detail by the following examples, but the invention is not limited to the examples. The evaluation method in the examples is as follows.

<polymerization conditions>

An ultra-high pressure mercury lamp of 250 W was used in a nitrogen atmosphere at room temperature, and light having an intensity of 30 mW/cm ² (365 nm) was irradiated for 30 seconds.

<Evaluation of horizontal alignment> (1) Fabrication of a glass substrate with a rubbed alignment film

Spinning a low pretilt angle (horizontal alignment mode) on a glass substrate having a thickness of 1.1 mm with polylysine (Lixon Aligner: PIA-5370, manufactured by JNC), drying the solvent on a hot plate at 80 ° C, and then drying at 230 After calcination in an oven at ° C for 30 minutes, rubbing treatment was carried out using a crepe cloth.

(2) Confirmation of liquid crystal alignment uniformity

The substrate with the liquid crystal film was placed between two polarizing plates arranged to be orthogonally polarized, and it was observed whether or not light leaked (transmits fine light) when the film was in a dark field. When the alignment of the liquid crystal has a defect, light leakage occurs. When there is no light leakage, it can be judged that the alignment is uniform.

<Evaluation of vertical alignment>

The substrate attached to the film can be used as it is without rubbing treatment.

The obtained liquid crystal film substrate is sandwiched between two polarizing plates arranged to be orthogonally polarized, and when it is confirmed that the substrate is viewed from the front, it is a dark field of view, and when viewed from the direction of the top, bottom, left, and right, it is a bright field, and the alignment of the liquid crystal frame is indicated. The vector is perpendicular to the glass substrate and can be judged as vertical alignment. The uniformity of the vertical alignment is such that the two polarizing plates are in a state of being orthogonally polarized, and when a liquid crystal film substrate is placed therebetween and viewed from the front, light leakage from the alignment defect of the liquid crystal cannot be visually confirmed (dark field of view). The state is a state of uniform alignment.

<Measurement by Polarization Analysis Device: Confirmation of Orientation Pattern>

The liquid crystal film substrate was irradiated with light having a wavelength of 550 nm using an OPTIPRO polarizing analyzer manufactured by Shintech Co., Ltd. The incident angle of the light was gradually decreased from 90 degrees with respect to the film surface, and the retardation value was measured to confirm the alignment form in which the direction in which the irradiation was inclined coincided with the rubbing direction (the long-axis direction of the liquid crystal molecules). When the delay value from the vertical direction is the maximum, it is judged that the alignment is horizontal. In the horizontal alignment, the alignment vector of the liquid crystal molecules is parallel to the support substrate. On the other hand, when the delay value from the vertical direction is the smallest, it is judged that the alignment is vertical. In the vertical alignment, the alignment vector of the liquid crystal molecules is perpendicular to the support substrate.

The retardation (phase delay) is represented by Δ n ×d. △ n is a refractive index anisotropy, d is the thickness of the polymer film (film thickness).

<film thickness measurement>

The liquid crystal film layer with the liquid crystal film glass substrate was cut off, and the step was measured using a fine shape measuring device (Alpha Step IQ, manufactured by KLA TENCOR Co., Ltd.).

<Evaluation of optical anisotropy (Δ n )>

The retardation and the film thickness value obtained from the liquid crystal film aligned horizontally were calculated by the retardation/film thickness.

The compounds used in the examples and comparative examples are shown below.

Compound (1-1-3) can be synthesized by the following method.

(The first stage)

2470 mmol of trans-p-hydroxycinnamic acid and 10 mL of concentrated sulfuric acid were added to 1200 mL of methanol, and the mixture was stirred under heating for 5 hours. The solvent was distilled off under reduced pressure. The obtained residue was poured into ice water, and ethyl acetate was added thereto for extraction. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol to give 2157 mmol of compound (ex-1).

(second stage)

561 mmol of the compound (ex-1), 617 mmol of sodium hydroxide and 56 mmol of sodium iodide were added to 1000 mL of N,N-dimethylformamide (DMF), and the mixture was stirred under a nitrogen atmosphere at 60 °C. 617 mmol of 6-chlorohexanol was added dropwise thereto. After the dropwise addition, the mixture was stirred at 80 ° C for 8 hours. Ethyl acetate and water were added to the reaction mixture for extraction. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The obtained residue and 617 mmol of sodium hydroxide were added to a mixed solution of 500 ml of water and 500 ml of methanol, and the mixture was stirred under reflux for 3 hours. The solvent was distilled off under reduced pressure, and the obtained residue was poured into 3N hydrochloric acid to reprecipitate. The crystals were separated by filtration and then recrystallized from ethanol to give compound (ex-2) 356 mmol.

(The third stage)

290 mmol of the compound (ex-2) and 551 mmol of dimethylaniline were added to 400 mL of toluene, and the mixture was stirred at room temperature under a nitrogen atmosphere. 348 mmol of acrylonitrile chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at 50 ° C for 4 hours. The reaction solution was poured into ice water, ethyl acetate was added for extraction, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was recrystallized from toluene to give Compound (ex-3) 118 mmol.

(fourth stage)

63 mmol of the compound (ex-3), 31 mmol of 9-methyl-2,7-dihydroxyindole and 13 mmol of 4-dimethylaminopyridine (DMAP) were added to 200 ml of dichloromethane, and the mixture was stirred under a nitrogen atmosphere. 30 mL of a solution of 66 mmol of 1,3-dicyclohexylcarbodiimide (DCC) in dichloromethane was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 8 hours. The precipitate was separated by filtration, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography, and recrystallized from ethanol to give 20 mmol of the above compound (1-1-3). The phase transition temperature is as follows.

Phase transition temperature: C 74 N 250<I

¹ H-NMR (CDCl ₃ ; δ ppm): 7.85 (d, 2H), 7.73 (d, 2H), 7.31 (s, 2H), 7.16 (d, 2H), 6.93 (d, 4H), 6.53 (d) , 2H), 6.41 (d, 2H), 6.16 to 6.09 (m, 2H), 5.83 (d, 2H), 4.18 (t, 4H), 4.01 (t, 2H), 1.87 to 1.80 (m, 4H), 1.76~1.69 (m, 4H), 1.70 (m, 2H), 1.57~1.43 (m, 11H).

The compounds (2-1-C3), (2-1-D3), and (2-1-A4) can be synthesized by the methods described in JP-A-2003-238491 and JP-A-2006-307150.

The compounds (2-2-1-2) and (2-2-26-2) can be synthesized in accordance with the method described in the specification of International Publication No. 2008/136265.

The compound (3-4-3) can be synthesized by the method described in Makromol. Chem., 190, 2255-2268 (1989). Compound (3-7-2) can be synthesized by the following method.

(The first stage)

322 mmol of methyl hydroquinone, 644 mmol of 4-hydroxybenzoic acid, 10 mmol of boric acid, and 1 mL of concentrated sulfuric acid were added to 400 mL of toluene, and the mixture was stirred for 8 hours while dehydrating under heating under reflux using Dean-Stark. The crystals were separated by filtration and recrystallized from ethanol to give compound (ex-4) 280 mmol.

(second stage)

16 mmol of the compound (ex-4) and 113 mmol of triethylamine were added to 40 ml of acetone, and the mixture was cooled and stirred under a nitrogen atmosphere at 5 °C. 50 mL of a toluene solution of 65 mmol of fumaric acid chloride was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then add dropwise 49 mmol of toluene of 4-hydroxybutyl acrylate 20 mL of liquid. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. The organic layer was extracted by adding a 2N hydrochloric acid solution to the reaction mixture. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by column chromatography, and recrystallized from ethanol to give 6 mmol of the compound (3-7-2). The phase transition temperature is as follows.

Phase transfer temperature: C 84 N 250<I

¹ H-NMR (CDCl ₃ ; δ ppm): 8.30 (d, 2H), 8.28 (d, 2H), 7.34 (d, 2H), 7.33 (d, 2H), 7.21 (d, 1H), 7.16 (d) , 1H), 7.13~7.10 (m, 1H), 7.09 (d, 4H), 6.43 (d, 2H), 6.18~6.10 (m, 2H), 5.87 (d, 2H), 4.31 (t, 4H), 4.23 (t, 4H), 2.27 (s, 3H), 1.89 to 1.78 (m, 8H).

The compound (3-9-2) can be synthesized according to the method described in the specification of U.S. Patent No. 5,770,107 and JP-A-2004-231638.

The compounds (3-10-2) and (3-11-2) can be synthesized by the methods described in JP-A-2006-225607 and 2007-16213.

The compound (4-1-2) can be synthesized by the method described in Macromolecules, 3938-3943, (23), 1990.

The compounds (4-4-1) and (4-4-2) can be synthesized by the method described in Makromol. Chem., 183, 2311-2321 (1982).

[Example 1] [Modulation of Polymerizable Liquid Crystal Composition (1)]

The composition MIX1 was mixed in a weight ratio of the compound (1-1-3): the compound (2-1-A4): the compound (4-1-2) = 35:30:35, and a polymerization ratio of 0.06 by weight was added thereto. Starting agent Irgacure Oxe01 (manufactured by BASF Japan) and A fluorine-based nonionic surfactant FTX-218 (manufactured by Neos) having a weight ratio of 0.01. Toluene/2-propanol = 9/1 (weight ratio) was added to the composition to prepare a polymerizable liquid crystal composition (1) having 16% by weight of MIX1.

Next, a low pretilt angle (horizontal alignment mode) was applied to a glass substrate (Matsunami Slide Glass: S-1112) using polylysine (Lixon Aligner: PIA-5370, manufactured by JNC Corporation), and dried at 80 ° C for 3 minutes. The mixture was calcined at 230 ° C for 30 minutes, and rubbed with a bismuth alignment cloth. The polymerizable liquid crystal composition (1) was continuously spin-coated on a rubbed glass substrate with a polyamic acid film. The substrate was heated at 80 ° C for 2 minutes, and cooled at room temperature for 2 minutes, and the coating film from which the solvent was removed was polymerized by ultraviolet rays under a nitrogen stream to obtain a liquid crystal film. When the obtained liquid crystal film substrate was placed between two polarizing plates arranged to be orthogonally polarized, and the substrate was in a dark field state, it was confirmed that no light leaked, and it was judged that the alignment was uniform. The retardation value of the liquid crystal film substrate was measured, and as a result, as shown in Fig. 1, the alignment was judged to be horizontal because the retardation value from the vertical direction was the largest. Further, the retardation measurement value at 90 degrees with respect to the film surface was 135 nm, and the film thickness was 563 nm, whereby Δ n was calculated to be 0.24.

[Comparative Example 1]

The following compound (β) was synthesized by the method described in JP-A-2006-111571.

The compound (3-4-3): Compound (4-1-2): Compound (β) = 40:35:25 by weight was mixed, and the composition MIX2 was obtained in the same manner as in Example 1. The polymerizable liquid crystal composition (2) was prepared as in Example 1 except that MIX2 was used to form a liquid crystal film. As a result, a horizontal alignment as in Example 1 was obtained, and as shown in Example 1, Δ n was calculated to be 0.15, which was not a large refractive index difference. Directional.

From the above results, it is understood that large refractive index anisotropy is easily obtained by using the compounds (1) and (2).

[Example 2]

In the MIX1 of Example 1, a compound ( α -2) having a weight ratio of 0.10, a 3-aminopropyltriethoxydecane (manufactured by JNC Corporation, trade name: Sila-Ace S-330) and a weight ratio of a weight ratio of 0.10 were mixed. The polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) of 0.03 was added with toluene/2-propanol = 9/1 (weight ratio) to prepare a polymerizable liquid crystal composition (3) having MIX1 of 20% by weight.

A low pretilt angle (horizontal alignment mode) was applied to a glass substrate (Matsunami Slide Glass: S-1112) using polylysine (Lixon Aligner: PIA-5370, manufactured by JNC Corporation), and dried at 80 ° C for 3 minutes and then at 230 The mixture was calcined at ° C for 30 minutes to form a substrate for evaluation. Next, the polymerizable liquid crystal composition (3) was spin-coated on a glass substrate with a polyimide film. The substrate was heated at 80 ° C for 2 minutes, and cooled at room temperature for 2 minutes, and the coating film from which the solvent was removed was polymerized under a nitrogen stream by ultraviolet rays to obtain a liquid crystal film. The obtained liquid crystal film substrate was placed between two polarizing plates arranged to be orthogonally polarized, and when the substrate was in a dark field state, it was confirmed that no light leaked, and it was judged that the alignment was uniform. The retardation value of the liquid crystal film-attached substrate was measured. As a result, as shown in Fig. 2, since the retardation value from the vertical direction was the smallest, it was judged that the alignment was vertical. Moreover, relative to the membrane The 45-degree retardation measurement was 51 nm and the film thickness was about 1.6 μm.

[Comparative Example 2]

A polymerizable liquid crystal composition (4) was prepared in the same manner as in Example 2 except that MIX2 of Comparative Example 1 was used to obtain a liquid crystal film. The obtained liquid crystal film substrate was placed between two polarizing plates arranged to be orthogonally polarized, and when the substrate was in a dark field state, no light leakage was observed, and it was judged that the alignment was uniform. The retardation value of the liquid crystal film substrate was measured, and as a result, as shown in Fig. 2, the alignment was judged to be vertical because the retardation value from the vertical direction was the smallest. Further, the retardation measurement value of 45 degrees with respect to the film surface was 37 nm, and the film thickness was about 1.6 μm. From this, it is understood that the retardation of the large vertical alignment liquid crystal film can be obtained by using the compounds (1) and (2).

[Example 3]

MIX3 is mixed in a weight ratio of compound (1-1-3): compound (2-1-D3)=70:30, and the solvent is cyclopentanone/propylene glycol monomethyl ether acetate (PGMEA)=9/1 ( The weight ratio of MIX3 was 16 wt%, and the polymerizable liquid crystal composition (5) was prepared in the same manner as in Example 1, and a liquid crystal film was formed by the method of Example 1, to obtain a liquid crystal film having a uniform horizontal alignment. The retardation value of the film was measured, and the same result as in Fig. 1 was obtained, and Δ n was calculated to be 0.23.

[Example 4]

The compound (1-1-3): compound (2-1-D3): compound (4-1-2) = 60:20:20 by weight ratio, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The object (6) forms a liquid crystal film to obtain a liquid crystal film having a uniform horizontal alignment. The retardation value of the film was measured, and the same result as in Fig. 1 was obtained, and Δ n was calculated to be 0.23.

[Example 5]

The compound (1-1-3): compound (2-1-A4): compound (2-1-D3) = 60:20:20 by weight ratio, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The substance (7) forms a liquid crystal film to obtain a liquid crystal film having a uniform horizontal alignment. The retardation value of the film was measured, and the same result as in Fig. 1 was obtained, and Δ n was calculated to be 0.24.

[Example 6]

The compound (1-1-3): compound (2-1-A4) = 70:30 by weight was mixed, and the polymerizable liquid crystal composition (8) was prepared as in the method of Example 1 to form a liquid crystal film, and as a result, A uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.26.

[Example 7]

The compound (1-1-3): compound (2-1-A4) = 50:50 by weight was mixed, and the polymerizable liquid crystal composition (9) was prepared in the same manner as in Example 1 to form a liquid crystal film. A uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.24.

[Example 8]

The compound (1-1-3): compound (2-2-26-2) = 50:50 by weight is mixed, and the polymerizable liquid crystal composition (10) is prepared as in the method of Example 1, to form a liquid crystal film. As a result, a liquid crystal film having a uniform horizontal alignment was obtained. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.20.

[Example 9]

The compound (1-1-3): compound (2-1-C-3) = 50:50 by weight is mixed, and the polymerizable liquid crystal composition (11) is prepared as in the method of Example 1, to form a liquid crystal film. As a result, a liquid crystal film having a uniform horizontal alignment was obtained. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.24.

[Example 10]

The compound (1-1-3): compound (2-2-1-2) = 50:50 by weight is mixed, and the polymerizable liquid crystal composition (12) is prepared as in the method of Example 1, to form a liquid crystal film. As a result, a liquid crystal film having a uniform horizontal alignment was obtained. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.22.

[Example 11]

The compound (1-1-3): compound (2-1-A4): compound (4-1-2) = 50:25:25 by weight ratio, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The substance (13) forms a liquid crystal film to obtain a uniform horizontal alignment liquid crystal film. The retardation value of this film was measured, and the result was the same as that of Fig. 1, and Δ n was calculated to be 0.24.

[Example 12]

The compound (1-1-3): compound (2-1-A4): compound (2-1-C3): compound (4-1-2) = 50:20:10:20 by weight ratio, in addition The polymerizable liquid crystal composition (14) was prepared in the same manner as in the method of Example 1, and a liquid crystal film was formed to obtain a liquid crystal film of a uniform horizontal alignment. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.20.

[Example 13]

The compound (1-1-3): compound (2-1-A4): compound (4-4-2) = 50:20:30 by weight ratio, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The object (15) forms a liquid crystal film to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, it was calculated as Δ n of 0.23 as in Fig. 1 .

[Example 14]

The compound (1-1-3): compound (2-1-A4): compound (4-4-1) = 50:25:25 by weight ratio, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The object (16) forms a liquid crystal film to obtain a uniform horizontal alignment liquid crystal film. The retardation value of this film was measured, and the result was the same as that of Fig. 1, and Δ n was calculated to be 0.24.

[Example 15]

The compound (1-1-3): compound (2-1-A4): compound (3-11-2) = 30:20:50 by weight ratio, and the polymerizable liquid crystal composition was prepared by the method of Example 1. (17) A liquid crystal film is formed to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as in Fig. 1, Δ n was calculated to be 0.26.

[Example 16]

The compound (1-1-3): compound (2-1-A4): compound (3-10-2) = 30:20:50 by weight ratio, and the polymerizable liquid crystal composition was prepared by the method of Example 1. (18) A liquid crystal film is formed to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as in Fig. 1, Δ n was calculated to be 0.24.

[Example 17]

The compound (1-1-3): compound (2-1-A4): compound (3-9-2) = 30:20:50 by weight ratio, and the polymerizable liquid crystal composition was prepared by the method of Example 1. (19) A liquid crystal film is formed to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.23.

[Example 18]

The compound (1-1-3): compound (2-1-A4): compound (3-7-2) = 30:20:50 by weight ratio was mixed, and the composition of the polymerizable liquid crystal was adjusted as in the method of Example 1. The object (20) forms a liquid crystal film to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, it was calculated as Δ n of 0.23 as in Fig. 1 .

[Example 19]

Mixed with the weight ratio of the compound (1-1-3): compound (2-1-A4): compound (3-11-2): compound (4-1-2) = 40:20:20:20, The polymerizable liquid crystal composition (21) was prepared as in the method of Example 1, and a liquid crystal film was formed to obtain a uniform horizontal alignment liquid crystal film. The retardation value of the film was measured, and as a result, as shown in Fig. 1, Δ n was calculated to be 0.25.

[Industry Utilization]

When the polymerizable liquid crystal composition of the present invention is used, a liquid crystal film having a uniform horizontal alignment form or a vertical alignment form can be obtained, and the refractive index anisotropy of the obtained liquid crystal film is relatively large.

Fig. 1 is a result of measurement of retardation of the liquid crystal film (horizontal alignment) of Example 1.

2 is a measurement result of retardation of the liquid crystal film (vertical alignment) obtained in Example 2 and Comparative Example 2.

Claims (15)

A polymerizable liquid crystal composition comprising: a component (A) selected from at least one compound of the group of compounds represented by the formula (1); and a component (B) selected from the group of compounds of the formula (2-1) At least one compound; and component (C), the component (C) being at least one compound selected from the group of compounds of the formula (3); In the formula (1), W ^{11 is} independently hydrogen, methyl or ethyl; W ^{12 is} independently hydrogen or an alkyl group having 1 to 7 carbon atoms; X ^{1 is} independently hydrogen or methyl; Y ^{1 is} independently a carbon number 1 ~20 alkylene, any -CH ₂ - may be substituted by -O-; In the formula (2-1), X ^{2A is} independently hydrogen, methyl or trifluoromethyl; W ^{21A is} independently hydrogen, fluorine, chlorine, methyl or ethyl; W ^{22A is} independently hydrogen or halogen; n ^{2A is} independently Is an integer from 2 to 10; Z ^{21A is} independently a single bond, -CH ₂ CH ₂ -; In the formula (3), X ^{3 is} independently hydrogen, methyl or trifluoromethyl; W ^{31 is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or C 1-7 alkoxy Any of the alkyl and alkoxy groups may be substituted by fluorine; r is an integer from 0 to 4; W ^{32 is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or carbon number 1-7 alkoxy group, any hydrogen in the alkyl group and alkoxy group may be substituted by fluorine; n ^{31 is} independently an integer of 2 to 10; n ³² is an integer of 1 to 3; Z ^{31 is} independently a single bond, - O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO-CH=CH-COO- or -OCOO-; Z ^{32 is} independently a single bond, -CH ₂ CH ₂ -or- CH=CH-. The polymerizable liquid crystal composition according to claim 1, wherein in the formula (1) described in the first paragraph of the patent application, W ^{11 is} independently hydrogen, methyl or ethyl; and W ^{12 is} independently hydrogen. Or an alkyl group having 1 to 3 carbon atoms; X ^{1 is} independently hydrogen or methyl; Y ^{1 is} independently an alkylene group having 1 to 12 carbon atoms, and any -CH ₂ - may be substituted by -O-; In the formula (2-1) described in the first item, X ^{2A is} independently hydrogen or methyl; W ^{21A is} independently hydrogen, methyl or ethyl; W ^{22A is} independently hydrogen or halogen; n ^{2A is} independently 2 to 10 An integer of Z ^{21A is} independently a single bond, -CH ₂ CH ₂ -. The polymerizable liquid crystal composition according to claim 1, wherein in the formula (1) described in the first aspect of the patent application, W ^{11 is} independently hydrogen or methyl; and W ^{12 is} independently hydrogen or methyl. X ^{1 is} independently hydrogen or methyl; Y ^{1 is} independently an alkylene group having 1 to 10 carbon atoms, wherein any -CH ₂ - may be substituted by -O-; in the formula described in claim 1 ( In 2-1), X ^{2A is} independently hydrogen or methyl; W ^{21A is} independently hydrogen or methyl; W ^{22A is} independently hydrogen or fluorine; n ^{2A is} independently an integer from 2 to 10; Z ^{21A is} independently a single bond or - CH ₂ CH ₂ -. The polymerizable liquid crystal composition according to claim 1, further comprising a component (D) which is at least one compound selected from the group consisting of compounds of the formula (4); X ⁴ is hydrogen, methyl or trifluoromethyl; R ⁴ is cyano, -OCF ₃ , alkyl having 1 to 10 carbon atoms or alkoxy having 1 to 10 carbon atoms, and the alkyl group and alkoxy group are Any hydrogen may be substituted by fluorine; W ^{41 is} independently hydrogen, halogen, nitro, cyano, C 1-7 alkyl or C 1-7 alkoxy, any of the alkyl and alkoxy Can be substituted by fluorine; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond, -COO-, -OCO-, -CH=CH-COO-, - OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ - or -C≡C-; n ⁴¹ is an integer from 2 to 10; n ⁴² is an integer from 1 to 2. The polymerizable liquid crystal composition according to claim 4, wherein in the formula (4) described in claim 4, X ⁴ is hydrogen or methyl; R ⁴ is cyano, -OCF ₃ An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; W ^{41 is} independently hydrogen, fluorine, chlorine, nitro, cyano group, alkyl group having 1 to 3 carbon atoms or carbon number 1 to 3 Alkoxy group, any of the alkyl and alkoxy groups may be substituted by fluorine; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond, - COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ - or -C≡C-; n ⁴¹ is An integer from 2 to 10; n ⁴² is an integer from 1 to 2. The polymerizable liquid crystal composition according to claim 4, wherein in the formula (4) described in claim 4, X ⁴ is hydrogen or methyl; R ⁴ is cyano, -OCF ₃ An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; W ^{41 is} independently hydrogen, fluorine, methyl or methoxy, and any hydrogen in the methyl group and methoxy group may be substituted by fluorine ; Z ⁴¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁴² is a single bond, -COO-, -OCO-, -CH=CH-COO-, -CH ₂ CH ₂ -COO- or -C≡C-; n ⁴¹ is an integer from 2 to 10; n ⁴² is an integer from 1 to 2. The polymerizable liquid crystal composition according to claim 1, wherein in the formula (3) described in the first paragraph of the patent application, X ^{3 is} independently hydrogen or methyl; W ^{31 is} independently hydrogen, fluorine, a chlorine, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and any hydrogen in the alkyl group and the alkoxy group may be substituted by fluorine; r is an integer of 0 to 2 ; W ^{32 is} independently hydrogen, halogen, nitro, cyano, C 1 to 3 alkyl or C 1 to 3 alkoxy, and any of the alkyl and alkoxy may be substituted by fluorine; n ³¹ Independently an integer from 2 to 10; n ³² is an integer from 1 to 3; Z ^{31 is} independently a single bond, -O-, -CO-, -CH=CH-, -COO-, -OCO-, -OCO-CH =CH-COO- or -OCOO-; Z ^{32 is} independently a single bond, -CH ₂ CH ₂ - or -CH=CH-. The polymerizable liquid crystal composition according to claim 1, wherein in the formula (3) described in the first paragraph of the patent application, X ^{3 is} independently hydrogen or methyl; W ^{31 is} independently hydrogen, fluorine, Cyano, methyl or methoxy, any hydrogen in the methyl and methoxy groups may be substituted by fluorine; r is an integer from 0 to 2; W ^{32 is} independently hydrogen, fluorine, cyano, methyl or methoxy Any one of the methyl and methoxy groups may be substituted by fluorine; n ^{31 is} independently an integer from 2 to 10; n ³² is an integer from 1 to 3; and Z ^{31 is} independently a single bond, -O-, -CO -, - CH = CH -, - COO -, - OCO -, - OCO-CH = CH-COO- or -OCOO-; Z ³² is independently a single bond, -CH ₂ CH ₂ - or -CH = CH-. The polymerizable liquid crystal composition according to claim 1, which further comprises a nonionic surfactant. The polymerizable liquid crystal composition according to claim 9, wherein the nonionic surfactant is a fluorine-based, anthrone-based or hydrocarbon-based nonionic surfactant. The polymerizable liquid crystal composition according to claim 4, wherein the component (A) is from 1 to 99% by weight based on the total weight of the components (A) to (D), and the component ( B) is 1 to 99% by weight, the component (C) is 0 to 98% by weight, and the component (D) is 0 to 70% by weight. The polymerizable liquid crystal composition according to claim 4, wherein the component (A) is 3 to 95% by weight based on the total weight of the components (A) to (D), and the component ( B) is 3 to 95% by weight, the component (C) is 0 to 94% by weight, and the component (D) is 0 to 50% by weight. The polymerizable liquid crystal composition according to claim 4, wherein the component (A) is 5 to 90% by weight based on the total weight of the components (A) to (D), and the component ( B) is 5 to 90% by weight, the component (C) is 0 to 90% by weight, and the component (D) is 0 to 40% by weight. An optically anisotropic body obtained by polymerizing at least one of the polymerizable liquid crystal compositions according to claim 1 of the patent application. A liquid crystal display element comprising the optically anisotropic body according to claim 14 of the patent application.