JP6015988B2 - Polymerizable liquid crystal composition and optical anisotropic body - Google Patents

Description

  The present invention relates to a polymer obtained by polymerizing a liquid crystal composition containing a polymerizable liquid crystal compound, a polymer having optical anisotropy (optical anisotropic body) obtained using this polymer, and the optical heterogeneity. The present invention relates to a liquid crystal display element containing a rectangular parallelepiped.

  In recent years, polymerizable liquid crystal compounds have been used for optically anisotropic materials such as polarizing plates, polarizing reflectors, and retardation plates. This is because this compound exhibits optical anisotropy in a liquid crystal state, and this anisotropy is fixed by polymerization. Since the optical properties necessary for the optical anisotropic body vary depending on the purpose, a compound having the properties suitable for the purpose is required. Since a compound used for an optical anisotropic body is often difficult to control the anisotropy alone, it may be used as a composition in combination with various compounds.

  The present inventors have developed a polymerizable liquid crystal compound (Patent Documents 1 to 3) having a fluorene skeleton. A polymerizable liquid crystal composition using these compounds may be used as an ink to which an organic solvent is added for the purpose of adjusting the coating property. In order to produce a film having optical anisotropy using a polymerizable liquid crystal composition, a polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant, etc. are dissolved in an organic solvent, and the solution viscosity, leveling property, etc. are adjusted. Prepare the adjusted ink. The ink is applied to an alignment-treated transparent substrate film, the solvent is dried, and the polymerizable liquid crystal composition is aligned on the substrate film. Next, the polymer is irradiated with ultraviolet rays to fix the alignment state. Here, when the tilt angle stability of the polymerizable liquid crystal composition is insufficient, scattering resulting from alignment defects may occur, and it may become impossible to obtain a transparent optically anisotropic body. In addition, from the viewpoint of the production process, when it is allowed to stand at room temperature for a long time after drying the solvent and until polymerization, recrystallization may occur, which may cause a poor appearance of the coating film. Furthermore, in a polarizing reflector using a cholesteric liquid crystal, a large refractive index anisotropy has been required for a polymerizable liquid crystal compound serving as a base in order to improve luminance (Patent Document 4). The polymerizable liquid crystal compound serving as a base in this case is a polymerizable liquid crystal compound that does not include an optically active site in the structure. It seems that the occurrence of various defects can be reduced when this polymerizable liquid crystal compound is horizontally aligned uniformly. Moreover, as a method for increasing the refractive index anisotropy, it is conceivable to introduce an unsaturated bond at the bonding site. A specific example in which an unsaturated bond is introduced into a bonding site of a polymerizable liquid crystal compound having a fluorene skeleton is described in Patent Document 5. Patent Document 5 discloses a polymerization compound having a homeotropic orientation and having a refractive index anisotropy small by using a polymerizable compound having a triptycene skeleton and a compound having a bisphenol skeleton and an amine silane coupling agent as essential components. The liquid crystal composition is intended to provide a liquid crystal composition, and the combination is different from the present invention.

JP 2003-238491 A JP 2005-60373 A International Publication No. 2008/136265 Pamphlet International Publication No. 2009/41512 Pamphlet JP 2010-163600 A

  The first object of the present invention is to provide a polymerizable liquid crystal composition that is easy to control the tilt angle, has a wide range of liquid crystal phase expression region, and has a low recrystallization temperature as it exhibits a liquid crystal phase even when left at room temperature. Is to provide. The second object is to provide an optical anisotropic body in which the orientation of the polymerizable liquid crystal film is uniform and according to the application. The third object is to provide a liquid crystal display element containing this optical anisotropic body.

  The present inventors have found that many of the above problems can be solved by using a polymerizable liquid crystal composition mainly composed of a cinnamate moiety and a fluorene-based polymerizable liquid crystal compound, and have completed the present invention. It was. The polymerizable liquid crystal composition of the present invention is shown in the following item [1].

[1] Component (A) which is at least one compound selected from the group of compounds represented by formula (1) and a group of compounds represented by formulas (2-1) to (2-2) A polymerizable liquid crystal composition containing the component (B), which is at least one compound.

In 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 carbons or alkoxy having 1 to 7 carbons;
X ¹ is independently hydrogen, methyl or trifluoromethyl;
Y ¹ is independently alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — may be —O—, —S—, —COO. -, -OCO-, -OCOO-, -CH = CH-, or -C≡C- may be substituted.

式（２−１）において、
Ｘ^２Ａは独立して水素、メチルまたはトリフルオロメチルであり；
Ｗ^２１Ａは独立して水素、フッ素、塩素、メチルまたはエチルであり；
Ｗ^２２Ａは独立して水素、ハロゲン、ニトロ、シアノまたは炭素数１〜７のアルキルまたはアルコキシであり；
ｎ^２Ａは独立して２〜１０の整数であり；
Ｚ^２１Ａは独立して単結合、−ＣＨ_２ＣＨ_２−であり；
式（２−２）において、
Ｘ^２Ｂは独立して水素、メチルまたはトリフルオロメチルであり；
Ｗ^２１Ｂは独立して水素、フッ素、塩素、メチルまたはエチルであり；
Ｚ^２３Ｂは独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−または−Ｃ≡Ｃ−であり；
Ｚ^２２Ｂは独立して単結合または−Ｏ−であり；
Ａ^２１Ｂは独立して１，４−シクロへキシレン、１，４−フェニレン、１，３−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイルまたはテトラヒドロナフタレン−２，６−ジイルであり、この１，３−フェニレンおよび１，４−フェニレンにおいて任意の水素は、フッ素、塩素、シアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチルまたはトリフルオロメチルで置き換えられてもよく；
Ｙ^２Ｂは独立して炭素数２〜２０のアルキレンであり、このアルキレンにおいて任意の水素はフッ素または塩素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。

In 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, cyano, or alkyl or alkoxy having 1 to 7 carbons;
n ^2A is independently an integer from 2 to 10;
Z ^21A is independently a single bond, —CH ₂ CH ₂ —;
In 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 a -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, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trimethyl May be replaced by fluoroacetyl, difluoromethyl or trifluoromethyl;
Y ^2B is independently an alkylene having 2 to 20 carbon atoms, and in this alkylene, any hydrogen may be replaced by fluorine or chlorine, and any —CH ₂ — may be —O—, —COO—, —OCO. -, -CH = CH- or -C≡C- may be substituted.

  The compound of formula (1), which is a fluorene-based polymerizable liquid crystal compound having a cinnamate moiety, is excellent in compatibility with other liquid crystal compounds and has a large refractive index anisotropy, so that it is useful as a component of a polymerizable liquid crystal composition. It is. The polymer of the present invention can be used for, for example, a retardation 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.

Retardation measurement result of the liquid crystal film (homogeneous alignment) obtained in Example 1 Retardation measurement results of liquid crystal films (homeotropic alignment) obtained in Example 2 and Comparative Example 2

Terms used in this specification are as follows. A liquid crystal compound is a generic term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase or the like, and often means a nematic phase. Polymerizability means the ability of a monomer to polymerize and give a polymer by means such as light, heat, or catalyst. The compound represented by formula (1) may be referred to as compound (1). The compounds represented by other formulas may be referred to according to the same simplified method. The meaning of the term “liquid crystalline” is not limited to having a liquid crystal phase. Even if it does not have a liquid crystal phase itself, a characteristic that can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound is also included in the meaning of liquid crystal. The term “arbitrary” used in describing the structure of a compound means that not only the position but also the number is arbitrary. And for example, the expression “any A may be replaced by B, C or D” means that any A is replaced by B, any A is replaced by C, and any A is D In addition to the case where it is replaced with, it is meant to include the case where a plurality of A are replaced with at least two of B to D. However, the definition that any —CH ₂ — may be replaced by —O— does not include such a replacement that results in a linking group —O—O—. Further, when arbitrary —CH ₂ — is replaced by —CH═CH— or —C≡C—, the number of carbons does not exceed the stated range. For example, Y ¹ in formula (1) is alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary —CH ₂ — may be replaced by —CH═CH— or —C≡C—, In this case, the carbon number of the alkylene including the substitution with CH═CH— or —C≡C— does not exceed 20. This rule is the same for other definitions.
A substituent in which the bonding position with the carbon constituting the ring is not clear means that the bonding position is free as long as there is no chemical problem. The optically active compound having a polymerizable group of the present invention may be referred to as a polymerizable optically active compound, an optically active compound, or simply a compound. Similarly, the polymerizable liquid crystal composition may be referred to as a liquid crystal composition or simply a composition. When the compound has one polymerizable group, it may be called monofunctional. Moreover, when a compound has two or more polymeric groups, it may be called by the name corresponding to the number of polyfunctionality or polymeric groups. The large refractive index anisotropy (Δn) in the present invention is 0.20 or more.

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

[2] In the formula (1) described in the item [1],
W ¹¹ is independently hydrogen, methyl or ethyl;
W ¹² is independently hydrogen, fluorine, chlorine, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons;
X ¹ is independently hydrogen or methyl;
Y ¹ is independently alkylene having 1 to 12 carbons, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO May be replaced by-, -OCOO-, -CH = CH- or -C≡C-;
In the formula (2-1) described in the term [1],
X ^2A is independently hydrogen or methyl;
W ^21A is independently hydrogen, methyl or ethyl;
W ^22A is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons;
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 term [1],
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 a -C≡C-;
Z ^22B is independently a single bond or —O—;
A ^21B is independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl; Any hydrogen in phenylene and 1,4-phenylene may be replaced by fluorine, chlorine, cyano, methyl, ethyl, methoxy, difluoromethyl or trifluoromethyl;
Y ^2B is independently alkylene having 2 to 10 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO -, -CH = CH- or -C≡C- may be substituted,
The polymerizable liquid crystal composition according to item [1].

[3] In the formula (1) described in the item [1],
W ¹¹ is independently hydrogen or methyl;
W ¹² is independently hydrogen, fluorine, chlorine, methyl or methoxy;
X ¹ is independently hydrogen or methyl;
Y ¹ is independently alkylene having 1 to 10 carbon atoms, and in this alkylene, any —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
In the formula (2-1) described in the term [1],
X ^2A is independently hydrogen or methyl;
W ^21A is 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 term [1],
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 a -C≡C-;
Z ^22B is independently a single bond or —O—;
A ^21B is independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, methyl, May be replaced by methoxy or trifluoromethyl;
Y ^2B is independently alkylene having 2 to 10 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine, and arbitrary —CH ₂ — represents —O—, —COO—, —OCO—, May be replaced by —CH═CH— or —C≡C—
The polymerizable liquid crystal composition according to item [1].

Ｘ^４は水素、メチルまたはトリフルオロメチルであり；
Ｒ^４はシアノ、−ＯＣＦ_３、炭素数１〜１０のアルキルまたは炭素数１〜１０のアルコキシであり、このアルキルおよびアルコキシにおいて任意の水素はフッ素で置き換えられてもよく；
環Ａ^４１は１，４−フェニレンまたは１，４−シクロヘキシレンであり；
Ｗ^４１は独立して水素、ハロゲン、ニトロ、シアノまたは炭素数１〜７のアルキルまたは炭素数１〜７のアルコキシであり、このアルキルおよびアルコキシにおいて任意の水素はフッ素で置き換えられてもよく、ただし、環Ａ^４１が１，４−シクロヘキシレンのとき、Ｗ^４１は水素であり；
Ｚ^４１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−または−ＯＣＯＯ−であり；
Ｚ^４２は単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−または−Ｃ≡Ｃ−であり；
ｎ^４１は２〜１０の整数であり；
ｎ^４２は１〜２の整数である。 [4] The polymerizability according to any one of items [1] to [3], further comprising a component (D) that is at least one compound selected from the group of compounds represented by formula (4): Liquid crystal composition.

X ⁴ is hydrogen, methyl or trifluoromethyl;
R ⁴ is cyano, —OCF ₃ , alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine;
Ring A ⁴¹ is 1,4-phenylene or 1,4-cyclohexylene;
W ⁴¹ is independently hydrogen, halogen, nitro, cyano, or alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine, provided that W ⁴¹ is hydrogen when Ring A ⁴¹ is 1,4-cyclohexylene;
Z ⁴¹ is a single bond, —O—, —COO—, —OCO— or —OCOO—;
Z ⁴² represents 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 of 1 to 2.

[5] In the formula (4) described in the item [4],
X ⁴ is hydrogen or methyl;
R ⁴ is cyano, —OCF ₃ , alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
Ring A ⁴¹ is 1,4-phenylene or 1,4-cyclohexylene;
W ⁴¹ is independently hydrogen, fluorine, chlorine, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine Provided that when ring A ⁴¹ is 1,4-cyclohexylene, W ⁴¹ is hydrogen;
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 of 1 to 2,
The polymerizable liquid crystal composition according to item [4].

[6] In the formula (4) described in the item [4],
X ⁴ is hydrogen or methyl;
R ⁴ is cyano, —OCF ₃ , alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
Ring A ⁴¹ is 1,4-phenylene or 1,4-cyclohexylene;
W ⁴¹ is independently hydrogen, fluorine, methyl or methoxy, and in this methyl and methoxy, any hydrogen may be replaced by fluorine, provided that when ring A ⁴¹ is 1,4-cyclohexylene, W ⁴¹ Is hydrogen;
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 of 1 to 2,
The polymerizable liquid crystal composition according to item [4].

式（３）において、
Ｘ^３は独立して水素、メチルまたはトリフルオロメチルであり；
Ｗ^３１は独立して水素、ハロゲン、ニトロ、シアノ、炭素数１〜７のアルキルまたは炭素数１〜７のアルコキシであり、このアルキルおよびアルコキシにおいて任意の水素はフッ素で置き換えられてもよく；
ｒは０〜４の整数であり；
Ｗ^３２は独立して水素、ハロゲン、ニトロ、シアノ、炭素数１〜７のアルキルまたは炭素数１〜７のアルコキシであり、このアルキルおよびアルコキシにおいて任意の水素はフッ素で置き換えられてもよく；
ｎ^３１は独立して２〜１０の整数であり；
ｎ^３２は１〜３の整数であり；
Ｚ^３１は独立して単結合、−Ｏ−、−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯ-ＣＨ＝ＣＨ-ＣＯＯ−または−ＯＣＯＯ−であり；
Ｚ^３２は独立して単結合、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。 [7] The polymerizability according to any one of items [1] to [6], further comprising a component (C) that is at least one compound selected from the group of compounds represented by formula (3) Liquid crystal composition.

In equation (3),
X ³ is independently hydrogen, methyl or trifluoromethyl;
W ³¹ is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine;
r is an integer from 0 to 4;
W ³² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with 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—.

[8] In the formula (3) described in the item [7],
X ³ is independently hydrogen or methyl;
W ³¹ is independently hydrogen, fluorine, chlorine, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine ;
r is an integer from 0 to 2;
W ³² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine;
n ³¹ is independently an integer from 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 item [7].

[9] In the formula (3) described in the item [7],
X ³ is independently hydrogen or methyl;
W ³¹ is independently hydrogen, fluorine, cyano, methyl or methoxy, in which any hydrogen may be replaced by fluorine;
r is an integer from 0 to 2;
W ³² is independently hydrogen, fluorine, cyano, methyl or methoxy, in which any hydrogen may be replaced by fluorine;
n ³¹ is independently an integer from 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 item [7].

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

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

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

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

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

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

[16] A liquid crystal display device having the optical anisotropic body according to item [15].

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

In equation (1),
W ¹¹ is independently hydrogen, fluorine, chlorine, methyl or ethyl, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl.
W ¹² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, preferably hydrogen, fluorine, chlorine, alkyl having 1 to 3 carbons or 1 carbon. ˜3 alkoxy, more preferably hydrogen, fluorine, chlorine, methyl or methoxy.
X ¹ is independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.
Y ¹ is independently alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — may be —O—, —S—, —COO. -, -OCO-, -OCOO-, -CH = CH-, or -C≡C- may be substituted. Preferably, it is alkylene having 1 to 12 carbons, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO—, —OCOO. -, -CH = CH- or -C≡C- may be substituted. More preferably, it is alkylene having 1 to 10 carbon atoms, and in this alkylene, arbitrary —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C≡C. It may be replaced with-.

  The composition of the present invention contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-2) as the component (B).

Ｘ^２Ａは独立して水素、メチルまたはトリフルオロメチルであり、好ましくは水素またはメチルである。
Ｗ^２１Ａは独立して水素、フッ素、塩素、メチルまたはエチルであり、好ましくは水素、メチルまたはエチルであり、より好ましくは水素またはメチルである。
Ｗ^２２Ａは独立して水素、ハロゲン、ニトロ、シアノ、炭素数１〜７のアルキルまたは炭素数１〜７のアルコキシである。好ましくは水素、ハロゲン、ニトロ、シアノ、炭素数１〜３のアルキルまたは炭素数１〜３のアルコキシであり、より好ましくは水素、フッ素、メチルまたはメトキシである。
ｎ^２Ａは独立して２〜１０の整数である。
Ｚ^２１Ａは独立して単結合、−ＣＨ_２ＣＨ_２−である。 In formula (2-1),

X ^2A is independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.
W ^21A is independently hydrogen, fluorine, chlorine, methyl or ethyl, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl.
W ^22A is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons. Preferred is hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and more preferred is hydrogen, fluorine, methyl or methoxy.
n ^2A is independently an integer of 2 to 10.
Z ^21A is independently a single bond, —CH ₂ CH ₂ —.

Ｘ^２Ｂは独立して水素、メチルまたはトリフルオロメチルであり、好ましくは水素またはメチルである。
Ｗ^２１Ｂは独立して水素、フッ素、塩素、メチルまたはエチルであり、好ましくは水素、メチルまたはエチルであり、より好ましくは水素またはメチルである。
Ｚ^２３Ｂは独立して単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−または−Ｃ≡Ｃ−である。好ましくは単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−または−Ｃ≡Ｃ−である。より好ましくは単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２ＣＨ_２−または−Ｃ≡Ｃ−である。
Ｚ^２２Ｂは独立して単結合または−Ｏ−である。 In formula (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—. 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 ) 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, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, It may be replaced with trifluoroacetyl, difluoromethyl, or trifluoromethyl. 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl is preferred. Any hydrogen in 4-phenylene may be replaced with fluorine, chlorine, cyano, methyl, ethyl, methoxy, difluoromethyl or trifluoromethyl. More preferred is 1,4-cyclohexylene, 1,4-phenylene or 1,3-phenylene, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, methyl, methoxy or tri- It may be replaced with fluoromethyl.

Y ^2B is independently an alkylene having 2 to 20 carbon atoms, and in this alkylene, any hydrogen may be replaced by fluorine or chlorine, and any —CH ₂ — may be —O—, —COO—, —OCO. -, -CH = CH- or -C≡C- may be substituted. Preferably, it is alkylene having 2 to 10 carbon atoms, in which arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO—, —CH ═CH— or —C≡C— may be substituted. More preferably, it is alkylene having 2 to 10 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine, and arbitrary —CH ₂ — represents —O—, —COO—, —OCO—, —CH═. It may be replaced by CH- or -C≡C-.

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

In the formula (4), X ⁴ is hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.
R ⁴ is cyano, —OCF ₃ , alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine. Preferred are cyano, —OCF ₃ , alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons.
Ring A ⁴¹ is 1,4-phenylene or 1,4-cyclohexylene.
W ⁴¹ is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine. Preferably, it is hydrogen, fluorine, chlorine, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine. More preferred is hydrogen, fluorine, methyl or methoxy, and in this methyl and methoxy, any hydrogen may be replaced by fluorine. However, when ring A ⁴¹ is 1,4-cyclohexylene, W ⁴¹ is hydrogen.
Z ⁴¹ is a single bond, —O—, —COO—, —OCO—, or —OCOO—.
Z ⁴² represents 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 of 2 to 10.
n ⁴² is an integer of 1 to 2.

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

In formula (3-1),
X ³ is independently hydrogen, methyl or trifluoromethyl, preferably hydrogen or methyl.
W ³¹ is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, arbitrary hydrogen may be replaced with fluorine. Preferably, it is hydrogen, fluorine, chlorine, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine. More preferably, it is hydrogen, fluorine, cyano, methyl or methoxy, and in this methyl and methoxy, any hydrogen may be replaced with fluorine.
r is an integer of 0 to 4, preferably an integer of 0 to 2.
W ³² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl or alkoxy, any hydrogen may be replaced with fluorine. Preferred are hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with fluorine. More preferred is hydrogen, fluorine, cyano, methyl or methoxy, and in this methyl and methoxy, any hydrogen may be replaced by fluorine.
n ³¹ is independently an integer of 2 to 10.
n ³² is an integer of 1 to 3 independently.
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 this invention may contain (C) component and (D) component each independently, and may contain these components together.

  The composition of the present invention may further contain a nonionic surfactant. Examples of nonionic surfactants are fluorine-based, silicone-based or hydrocarbon-based. Nonionic surfactants have the effect of improving the smoothness of the coating film.

  The composition of the present invention has a nematic or smectic liquid crystal phase at room temperature. When a solution obtained by dissolving the composition of the present invention in a solvent is coated on a plastic substrate that has been subjected to orientation treatment such as rubbing treatment or a support substrate whose surface is coated with a plastic thin film, to form a film, Homogeneous orientation or hybrid orientation. In addition, when a non-polymerizable or polymerizable optically active compound is added to the composition of the present invention, twist orientation is obtained. When a compound having a bisphenol skeleton and a monofunctional polymerizable liquid crystal compound are added to the composition of the present invention, homeotropic alignment is easily obtained.

The compounds used in the composition of the present invention will be described.
Compound (1) has a skeleton having a specific structure centered on a fluorene ring and two polymerizable groups. This compound exhibits liquid crystallinity, and since the polymer of the polymerizable liquid crystal compound has a three-dimensional structure, the polymer is harder than a compound having one polymerizable group. Moreover, since it has a cinnamate site as an unsaturated bond site, it exhibits a relatively large optical anisotropy.

  Compounds (2-1) to (2-2) are compounds having two polymerizable groups with a fluorene ring as the center, but have binding sites different from those of compound (1). Since the polymer of the polymerizable compound has a three-dimensional structure, the polymer is harder than a compound having one polymerizable group. This compound may or may not exhibit liquid crystallinity. Since this compound has a common central skeleton with the compound (1), it has an action of lowering the melting point of the polymerizable liquid crystal composition. Hereinafter, the compound (2-1) to (2-2) or a compound derived therefrom may be referred to as the compound (2).

  Compound (4) has a phenylene skeleton and one polymerizable group. This compound has the property of increasing the tilt angle of other liquid crystal molecules and the property of decreasing the melting point. The compound derived from the compound (4) may be generically referred to as the compound (4) in the future, like the compound (2).

  Compound (3) has a phenylene skeleton and two polymerizable groups. This compound depends on conditions such as a support substrate and an additive, but when applied to a rubbing-treated substrate with an alignment film polymer having no side chain, a nonionic surfactant is added to the liquid crystal composition. In some cases, it tends to be homogeneously oriented. Moreover, there exists a tendency which shows a liquid crystal phase in a wide temperature range. The compound derived from the compound (3) may be generically referred to as the compound (3) in the future like the compound (2).

  The composition of the present invention contains compounds (1), (2-1) to (2-2), (3), (4) and other polymerizable compounds different from the nonionic surfactant. Also good. This composition may contain a silane coupling agent in order to improve the adhesion between the coating film and the supporting substrate. This composition may contain additives such as a polymerization initiator and a photosensitizer suitable for the polymerization reaction. The composition may contain additives such as an ultraviolet absorber, an antioxidant, a radical scavenger, a light stabilizer, and a chain transfer agent in order to improve the properties of the polymer. This composition may contain an organic solvent. Organic solvents are useful for producing uniform thickness coatings.

The ratio of each component in the composition of the present invention will be described.
A desirable ratio of the component (A) is 1 to 99% by weight based on the total weight of the components (A) to (D). A more desirable ratio is 3 to 95% by weight. A more desirable ratio is from 5 to 90% by weight.

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

  A desirable ratio of the component (D) is 0 to 70% by weight based on the total weight of the components (A) to (D). A more desirable ratio is 0 to 50% by weight. A more desirable ratio is from 0 to 40% by weight.

  A preferable ratio in the case of adding the nonionic surfactant is 0.0001 to 0.03 in a weight ratio with respect to the total weight of the components (A) to (D).

  A preferable ratio in the case of adding the silane coupling agent is 0.01 to 0.15 in a weight ratio with respect to the total weight of the components (A) to (D). A more preferable range of the weight ratio is 0.03 to 0.10.

  When other polymerizable compounds are added, the preferred ratio is 0.01 to 0.50, preferably 0.03 to 0.30 in terms of the weight ratio to the total weight of the components (A) to (D). It is. When an additive such as a polymerization initiator is used, the amount used may be the minimum amount that achieves the purpose.

The combination of each component in the composition of this invention is demonstrated.
When forming a homogeneous orientation,
A combination of the component (A), the component (B) and the component (C),
A combination of the component (A), the component (B), the component (C), and the component (D) is preferable.
When adjusting the alignment uniformity or coating uniformity, it may be combined with a nonionic surfactant. When improving adhesiveness with a support base material, you may combine with a silane coupling agent. Moreover, you may further combine another polymeric compound about each combination.

  Next, a method for synthesizing compounds will be described. Compounds used in the present invention include Houben Weyl (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Syntheses (Johnson). It can be synthesized by combining synthetic methods in organic chemistry, such as those described in Wily & Sons, Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen).

  For the synthesis method of compound (1), the method described in US Pat. No. 5,770,107 can be referred to.

  Methods for synthesizing the compounds (2-1) to (2-2) are described in JP2003-238491A, JP2006-307150A, and International Publication No. 2008/136265 pamphlet.

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

  The synthesis method of the compound (3) is described in Makromol. Chem., 190, 3201-3215 (1989), Makromol. Chem., 190, 2255-2268 (1989), WO 97/00600, US Pat. No. 5,770,107. It is described in the specification, Japanese Patent Application Laid-Open No. 2004-231638, and the like.

  Next, component compounds are exemplified. Preferred examples of compound (1) are shown below.

式（１−１）〜（１−６）において、Ｘ^１は独立して水素、塩素、メチル、またはトリフルオロメチルであり、ｎ独立しては２〜２０の整数である。

In formulas (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 compound (2-1) are shown below.

式（２−１−Ａ）〜（２−１−Ｄ）において、Ｘ^２Ａは独立して水素、メチル、またはトリフルオロメチルであり、ｎ^２Ａは独立して２〜１０の整数である。

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

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

In formulas (2-2-1) to (2-236), X ^2B is independently hydrogen, methyl or trifluoromethyl, and n ^2B is independently an integer of 2 to 15.

Preferred examples of compound (4) are shown below.

In the formulas (4-1) to (4-13), X ⁴ is independently hydrogen or methyl, W ⁴¹ is independently hydrogen or fluorine, R ⁴ is alkyl having 1 to 7 carbons, carbon The number 1-7 is alkoxy or —OCF 3, and n ⁴¹ is an integer of 2 to 10.

  Preferred examples of compound (3) are shown below.

In formulas (3-1) to (3-11), X ³ is independently hydrogen, methyl or trifluoromethyl, W ³² is independently hydrogen or fluorine, and n ³¹ is an integer of 2 to 10 It is.

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

Next, a nonionic surfactant is illustrated.
Examples of silicone-based nonionic surfactants include polyflow ATF-2, granol 100, granol 115, granol 400, granol 410, granol 435 manufactured by Kyoeisha Chemical Co., Ltd. based on unmodified silicone or modified silicone. , Granol 440, Granol 450, Granol 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-34 , BYK-346, BYK-347, BYK-348, BYK-370, BYK-375, BYK-377, BYK-378, BYK-3500, BYK-3510, and a BYK-3570.

  Examples of fluorine-based nonionic surfactants are BYK-340, FT 251, 221 MH, FT 250, FTX-215M, FTX-218M, FTX-233M, FTX-245M, FTX-290M, FTX -209F, FTX-213F, Aftergent 222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, Aftergent 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 -F L, KB-F2M, KB-F2S, a KB-F3M, and KB-FaM.

  Examples of hydrocarbon-based nonionic surfactants include polyflow no. 3, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, Polyflow No. 99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, and BYK-Silclean3700.

The above-mentioned polyflow and granol are both names of products sold by Kyoeisha Chemical Co., Ltd. BYK is the name of a product sold by Big Chemie Japan. Footent, FTX and KB are names of products sold by Neos Co., Ltd.
Said surfactant may be used independently and may mix and use 2 or more.

  Next, other polymerizable compounds, additives, and organic solvents are exemplified. These compounds may be commercially available products. Examples of other polymerizable compounds are compounds having one polymerizable group, compounds having two polymerizable groups, and polyfunctional compounds having three or more polymerizable groups.

  Examples of compounds having one polymerizable group are styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl fatty acid (eg, vinyl acetate), α, β -Ethylenically unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl ester of (meth) acrylic acid (alkyl having 1 to 18 carbon atoms), (meth) acrylic acid Hydroxyalkyl ester (hydroxyalkyl having 1 to 18 carbon atoms), aminoalkyl ester of (meth) acrylic acid (aminoalkyl having 1 to 18 carbon atoms), ether oxygen-containing alkyl ester of (meth) acrylic acid (containing ether oxygen) Alkyl having 3 to 18 carbon atoms, such as methoxyethyl ester, ethoxyethyl Ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, and butyl carbyl ester), N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, pivalic acid Vinyl, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, dicyclo Pentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate Dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl Phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide, etc. A poly (alkylene glycol) mono (meth) acrylate ester or di (meth) acrylate ester, or a polyethylene glycol having a degree of polymerization of 1 to 100 whose end is capped with an alkyl group having 1 to 6 carbon atoms, Polypropylene glycol, And ethylene oxide and copolymers of polyalkylene glycol having a propylene oxide - a le mono (meth) acrylic acid ester.

Examples of compounds having two polymerizable groups are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodehydrate. Candiacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (Biscoat V # 700), polyethylene glycol diacrylate , And methacrylate compounds of these compounds, polymerizable bisphenolfluorene derivatives having a cardo structure represented by formulas (α-1) to (α-6) That. These compounds are suitable for further increasing the degree of curing of the polymer.

  Examples of compounds having three or more polymerizable groups are pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol EO-added tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate , Tris ((meth) acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Rate, dipentaerythritol monohydroxy penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, Biscoat V # 802 (number of functional groups = 8), a BISCOAT V # 1000 (functionality = average 14). “Biscoat” is a trade name of Osaka Organic Chemical Co., Ltd. Those having a functional group of 16 or more can be obtained by acrylating them using Boltorn H20 (16 functions), Boltorn H30 (32 functions), and Boltorn H40 (64 functions) sold by Perstorp Specialty Chemicals.

  In order to optimize the polymerization rate of the polymerizable liquid crystal composition, a known radical photopolymerization initiator may be used. A preferable addition amount of the radical photopolymerization initiator is 0.0001 to 0.20 in a weight ratio with respect to the total weight of the components (A) to (D). A more preferable range of this weight ratio is 0.001 to 0.15. A more preferable range is 0.01 to 0.15. Examples of photo radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-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 907 Cure 369, Irgacure 379, Irgacure 754, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870, Darocure 4265, Darocure MBF, Darocure TPO, Irgacure 784, Irgacure 754, Irgacure OXE01, and is Irgacure OXE02. Both Darocur and Irgacure are names of products sold by BASF Japan. Known sensitizers (isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate (Darocur EDB), 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA), etc.) may be added thereto.

The following radical photopolymerization initiators can also be used as the radical photopolymerization initiator.
p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benz Phenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture.

  One or more chain transfer agents can be added to the polymerizable liquid crystal composition to control the mechanical properties of the polymer. By using a chain transfer agent, the length of the polymer chain or the length of the two cross-linked polymer chains in the polymer film can be controlled. These lengths can also be controlled simultaneously. Increasing the amount of chain transfer agent decreases the polymer chain length. A preferred chain transfer agent is a thiol compound. Examples of monofunctional thiols are dodecanethiol, 2-ethylhexyl- (3-mercaptopropionate. Examples of multifunctional thiols are trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1), and 1,3, 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1) “Karenz” is Showa Denko KK Is the product name.

  A polymerization inhibitor can be added to the polymerizable liquid crystal composition in order to prevent the initiation of polymerization during storage. Known polymerization inhibitors can be used, but preferred examples include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric hydrazide (DPPH), benzothiazine, 4-nitrosodimethyl. Aniline (NIDI), o-hydroxybenzophenone.

  In order to improve the storage stability of the polymerizable liquid crystal composition, a polymerization inhibitor may be added. When radicals are generated in the composition or the composition solution, the polymerization reaction of the polymerizable compound is promoted. In order to prevent this, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor, a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphoric acid-based antioxidant can be used.

  In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and 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. “Tinubin” is a trade name of BASF Japan, and “Adeka Stub” is a trade name of Asahi Denka Co., Ltd.

  Examples of light stabilizers are Tinuvin 111FDL, 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 , Kimabsorb 944FL, Kimabsorb 944LD, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA- 87, Siasorb UV-3346 manufactured by Cytec, and Goodlight UV-3034 manufactured by Goodrich. “Kimasorb” is a trade name of BASF Japan.

  Examples of antioxidants are ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, manufactured by Asahi Denka Co., Ltd., Sumilizer BHT sold by Sumitomo Chemical Co., Ltd. Sumilyzer BBM-S, Sumilyzer GA-80, and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 sold by BASF Japan. You may use these commercial items.

  A silane coupling agent may be further added to the polymerizable liquid crystal composition in order to control the adhesion with the substrate. Specifically, vinyl trialkoxysilane, 3-isocyanatopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, N- (1,3-dimethylbutylidene) -3- ( Trialkoxysilyl) -1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrialkoxysilane and the like. Another example is dialkoxymethylsilane in which one of the alkoxy groups (three) is replaced by methyl in these compounds.

  The polymerizable liquid crystal composition may be applied directly to the substrate surface. However, usually, in order to facilitate the coating, the polymerizable liquid crystal composition is diluted with a solvent, or each component of the polymerizable liquid crystal composition is dissolved in the solvent to obtain a polymerizable liquid crystal composition and a solvent. A polymerizable liquid crystal composition solution is prepared and applied. This solvent can be used alone or in combination of two or more. Examples of solvents are ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, Halogenated aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

  Preferred examples of the ester solvent include alkyl acetate (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), ethyl trifluoroacetate, propion Alkyl (eg, methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg: methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), Dialkyl malonate (eg diethyl malonate), alkyl glycolate (eg methyl glycolate and ethyl glycolate), alkyl lactate (eg methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate and lactic acid) Ethylhexyl), monoacetin, a γ- butyrolactone and γ- valerolactone.

  Preferred examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethyl acetal, N-methylcaprolactam and dimethylimidazolidinone.

  Preferred examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n -Heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 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 glycol monoalkyl ether solvent include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether (eg: propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg: dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg: ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether Acetate (eg, diethylene glycol) Monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (eg, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (Example: dipropylene glycol monomethyl ether acetate) and diethylene glycol methyl ethyl ether.

  Preferred examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, and tetralin. It is. 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 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 solvent are ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, and 1-methoxy-2-propyl acetate.

  From the viewpoint of the solubility of the polymerizable liquid crystal compound, it is preferable to use an amide solvent, an aromatic hydrocarbon solvent, or a ketone solvent. Considering the boiling point of the solvent, an ester solvent, an alcohol solvent, an ether solvent, a glycol A combined use of a monoalkyl ether solvent is also preferred. Although there is no particular limitation regarding the selection of the solvent, when a plastic substrate is used as the supporting base, it is necessary to lower the drying temperature in order to prevent deformation of the substrate and to prevent the solvent from attacking the substrate. Solvents preferably used in such cases are aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, glycol monoalkyl ether solvents.

  The ratio of the solvent in the solution of the polymerizable liquid crystal composition is 50 to 95% based on the total weight of the solution. The lower limit of this range is a numerical 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 numerical value considering the economic viewpoint such as the solvent cost and the time and heat amount when the solvent is evaporated. A preferable range of this ratio is 60 to 90%, and a more preferable range is 70 to 85%.

  In the following description, a polymer (optical anisotropic body) obtained by polymerizing a polymerizable liquid crystal composition may be referred to as a liquid crystal film. The liquid crystal film can be obtained as follows. First, a solution of a polymerizable liquid crystal composition is applied on a support substrate and dried to form a coating film. The coating film is irradiated with light to polymerize the polymerizable liquid crystal composition, and the nematic alignment formed in the liquid crystal state by the composition in the coating film is fixed. Support substrates that can be used are glass and plastic films. Examples of plastic films are polyimide, polyamide imide, polyamide, polyether imide, polyether ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene Films such as naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified products thereof, epoxy resin, phenol resin, and cycloolefin resin.

  Examples of cycloolefin resins include, but are not limited to, norbornene resins and dicyclopentadiene resins. Among these, those having no unsaturated bond or hydrogenated unsaturated bond are preferably used. For example, hydrogenated products of ring-opening (co) polymers of one or more norbornene monomers, addition (co) polymers of one or more norbornene monomers, norbornene monomers and olefin monomers Addition copolymers with (ethylene, α-olefin, etc.), norbornene monomers and cycloolefin monomers (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and these Specific examples include modified products such as ZEONEX, ZEONOR (manufactured by ZEON Corporation), ARTON (manufactured by JSR Corporation), TOPAS (manufactured by Chicona Corporation), APEL (manufactured by Mitsui Chemicals), ESINA (Sekisui Chemical Co., Ltd.) And OPTOREZ (manufactured by Hitachi Chemical Co., Ltd.).

  These plastic films may be uniaxially stretched films or biaxially stretched films. These plastic films may be subjected to surface treatment such as hydrophilic treatment such as corona treatment or plasma treatment, or hydrophobic treatment. There are no particular restrictions on the method of hydrophilization treatment, but corona treatment or plasma treatment is preferred, and a particularly preferred method is plasma treatment. For the plasma treatment, a method described in JP 2002-226616 A, JP 2002-121648 A, or the like may be used. Further, an anchor coat layer may be formed in order to improve the adhesion between the liquid crystal film and the plastic film. As long as such an anchor coat layer enhances the adhesion between the liquid crystal film and the plastic film, there is no problem even if it is an inorganic or organic material. The plastic film may be a laminated film. Instead of plastic film, use a metal substrate such as aluminum, iron or copper with slit-shaped grooves on the surface, or a glass substrate such as alkali glass, borosilicate glass or flint glass whose surface is etched into a slit shape. You can also.

  When forming a homogeneous alignment and a hybrid alignment liquid crystal film on a supporting substrate such as a glass or plastic film prior to the formation of a coating film of the polymerizable liquid crystal composition, physical and mechanical properties such as rubbing are used. Surface treatment is performed. When a homeotropic alignment liquid crystal film is formed, surface treatment such as rubbing is often not performed, but rubbing treatment may be performed in order to prevent alignment defects. Any method can be used for the rubbing treatment, but usually a rubbing cloth made of materials such as rayon, cotton, polyamide, etc. is applied to a metal roll etc., while rotating the roll while in contact with the support substrate or polymer film. A method of moving, a method of moving the support substrate side while fixing the roll, and the like are employed. The rubbing treatment may be performed directly on the supporting substrate, or a polymer film may be provided on the supporting substrate in advance, and the rubbing treatment may be performed on the polymer coating. The rubbing process is as described above. Depending on the type of the supporting substrate, silicon oxide can be inclinedly deposited on the surface to impart orientation ability.

  Examples of coating methods for obtaining a uniform film thickness when applying a polymerizable liquid crystal composition or a solution thereof include spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, and spray. Coating method, meniscus coating method and die coating method. In particular, a wire bar coating method or the like in which a shear stress is applied to the liquid crystal composition at the time of application may be used for controlling the alignment of the liquid crystal composition without performing surface treatment of the substrate by rubbing or the like.

  When applying the solution of the polymerizable liquid crystal composition of the present invention, the solvent is removed after the application to form a polymerizable liquid crystal layer having a uniform film thickness, that is, a layer of the polymerizable liquid crystal composition, on the support substrate. The conditions for removing the solvent are not particularly limited. What is necessary is just to dry until a solvent is removed substantially and the fluidity | liquidity of the coating film of polymeric liquid crystal composition is lose | eliminated. The solvent can be removed using air drying at room temperature, drying on a hot plate, drying in a drying furnace, blowing warm air or hot air, and the like. Depending on the type and composition ratio of the compound used in the polymerizable liquid crystal composition, nematic alignment of the polymerizable liquid crystal composition in the coating film may be completed in the process of drying the coating film. Therefore, the coating film that has undergone the drying process can be subjected to the polymerization process without going through a heat treatment process to be described later.

  The temperature and time when heat-treating the coating, the wavelength of light used for light irradiation, the amount of light irradiated from the light source, etc. are the types and composition ratios of the compounds used in the polymerizable liquid crystal composition, and the addition of a photopolymerization initiator The preferred range varies depending on the presence or absence and the amount added. Accordingly, the conditions regarding the temperature and time of the heat treatment of the coating film described below, the wavelength of the light used for light irradiation, and the amount of light irradiated from the light source are merely an approximate range.

  The heat treatment of the coating film is preferably performed under conditions that remove the solvent and obtain uniform orientation of the polymerizable liquid crystal. You may carry out above the liquid crystal phase transition point of a polymeric 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 to form a nematic alignment in the polymerizable liquid crystal composition in the coating film. The nematic alignment may be formed by changing the temperature of the coating film within a temperature range in which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which a nematic orientation is substantially completed in a coating film by heating the coating film to a high temperature range of the above temperature range, and then the order is further ordered by lowering the temperature. Regardless of which of the above heat treatment methods is employed, the heat treatment temperature is from room temperature to 120 ° C. A preferable range of this temperature is room temperature to 100 ° C, a more preferable range is room temperature to 90 ° C, and a further preferable range is room temperature to 85 ° C. The heat treatment time is 5 seconds to 2 hours. A preferable range of this time is 10 seconds to 40 minutes, and a more preferable range is 20 seconds to 20 minutes. In order to raise the temperature of the layer made of the polymerizable liquid crystal composition to a predetermined temperature, the heat treatment time is preferably 5 seconds or more. In order not to lower the productivity, it is preferable to set the heat treatment time within 2 hours. In this way, the polymerizable liquid crystal layer of the present invention is obtained.

The nematic alignment state of the polymerizable liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by polymerizing the polymerizable liquid crystal compound by light irradiation. The wavelength of light used for light irradiation is not particularly limited. Electron beams, ultraviolet rays, visible rays, infrared rays (heat rays), etc. can be used. Usually, ultraviolet rays or visible rays may be used. The wavelength range is 150 to 500 nm. A preferable range is 250 to 450 nm, and a more preferable range is 300 to 400 nm. Examples of light sources are low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, mercury xenon lamps). is there. Preferred examples of the light source are a metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp, and a high pressure mercury lamp. The wavelength region of the irradiation light source may be selected by installing a filter or the like between the light source and the polymerizable liquid crystal layer and passing only a specific wavelength region. The amount of light irradiated from the light source is ² to 5000 mJ / cm ² when reaching the coating surface. A preferred range of light intensity is 10~3000mJ / cm ^2, and more preferred range is 100 to 2000 mJ / cm ^2. It is preferable that the temperature condition at the time of light irradiation is set similarly to the above heat treatment temperature. The atmosphere of the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere, and an air atmosphere, but a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving curability.

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

  One of the methods for controlling the tilt angle is a method for adjusting the type and composition ratio of the liquid crystal compound used in the polymerizable liquid crystal composition. The tilt angle can also be controlled by adding other components to the polymerizable liquid crystal compound. The tilt angle of the liquid crystal film can also be controlled by the kind and amount of the solvent in the polymerizable liquid crystal composition, the kind and 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 support substrate or polymer film, rubbing conditions, drying conditions of the coating film of the polymerizable liquid crystal composition, heat treatment conditions, and the like. Furthermore, the irradiation atmosphere in the photopolymerization step after alignment, the temperature at the time of irradiation, and the like also affect the tilt angle of the liquid crystal film. That is, it can be considered that almost all conditions in the manufacturing process of the liquid crystal film affect the tilt angle to some extent. Therefore, by optimizing the polymerizable liquid crystal composition and appropriately selecting various conditions for the production process of the liquid crystal film, an arbitrary tilt angle can be obtained.

  In the homogeneous orientation, the tilt angle is uniformly close to 0 degrees from the substrate interface to the free interface, and is particularly distributed in the range of 0 to 5 degrees. This alignment state is obtained by applying the polymerizable liquid crystal composition of the present invention containing the component (A), the component (B) and a nonionic surfactant as components to a support substrate surface that has been subjected to a surface treatment such as rubbing, It is obtained by forming a coating film.

  In the following description, “% by weight” indicating the proportion of the component (A) to the component (D) is based on the total weight of the component (A) to the component (D). In the present invention, in order to obtain uniform homogeneous alignment, it is preferable to use the component (A) in an amount of 1 to 99% by weight. A more preferable range of this ratio is 3 to 95% by weight. A more preferred range is 5 to 90% by weight. Preferred examples of compound (1) are compounds (1-1-1) to (1-2-6). A plurality of compounds represented by compound (1) may be used in combination.

  The proportion of component (B) used is preferably 1 to 99% by weight. A more preferable range of this ratio is 3 to 95% by weight. A more preferred range is 5 to 90% by weight. Preferred examples of compound (2) include compounds (2-1-A1) to (2-1-D5), compounds (2-2-1-1) to (2-2-10-2), compound (2 2-13-1) to (2-236-1). A plurality of compounds represented by compound (2) may be used in combination.

  The component (D) is not necessarily required, but when used for adjusting the melting point, the use ratio is 1 to 70% by weight, preferably 1 to 50% by weight. More preferably, it is 1 to 40% by weight. Preferred examples of compound (4) are compounds (4-1-1) to (4-13-2). A plurality of compounds represented by compound (4) may be used in combination.

The component (C) may be used for adjusting the optical anisotropy. A preferred ratio when the component (C) is used is 1 to 98% by weight. A more preferable range of this ratio is 1 to 94% by weight, and a further preferable range is 1 to 90% by weight.
Preferred examples of compound (3) include compounds (3-4-1) to (3-4-6), compounds (3-5-1) to (3-5-6), and compounds (3-6-1). ) To (3-11-4). A plurality of compounds represented by compound (3) may be used in combination.

The use ratio of the nonionic surfactant is in the range of 0.0001 to 0.03 by weight ratio with respect to the total weight of the components (A) to (D). A plurality of nonionic surfactants may be used in combination.

  If uniform homogeneous alignment is difficult to form, tilt alignment is considered strong, so the amount of component (C) is increased, the amount of component (D) is minimized, or the amount of nonionic surfactant is increased. By optimization, uniform homogeneous orientation is obtained.

The composition of the present invention may contain a liquid crystal compound having no polymerizable group. Examples of such non-polymerizable liquid crystal compounds are described in Licris, a database of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). Specific examples of the liquid crystal compound having no polymerizable group include those described in JP 2011-148762 A, p. 66-69. The polymerizable liquid crystal composition of the present invention has good compatibility with other liquid crystal compounds. Such a polymerizable liquid crystal composition may further contain additives such as a dichroic dye and a fluorescent dye. By polymerizing this polymerizable liquid crystal composition, a composite material with a liquid crystal compound having no polymerizable group can be obtained.

An optically active compound may be added to the composition of the present invention. Preferred examples of the optically active compound are compounds represented by formulas (Op-1) to (Op-25). In these formulas, Ak represents alkyl having 1 to 15 carbons or alkoxy having 1 to 15 carbons, and Me, Et and Ph represent methyl, ethyl and phenyl, respectively. P ² is a polymerizable group, and is preferably a group containing (meth) acryloyloxy, vinyloxy, oxiranyl, or oxetanyl. The composition of the present invention may be used as a raw material of a polymer described below, or as a liquid crystal that is a constituent element of a liquid crystal display element.

As a specific example, p. 70, paragraphs 0159-p. 81, paragraph 0170.

  By polymerizing a polymerizable liquid crystal composition containing a suitable amount of a compound having optical activity or a polymerizable liquid crystal composition containing a suitable amount of a polymerizable compound having optical activity on an alignment-treated substrate. A retardation film showing a helical structure (twist structure) is obtained. The helical structure is fixed by polymerization of the polymerizable liquid crystal composition. The properties of the obtained liquid crystal film depend on the helical pitch of the obtained helical structure. The helical pitch length can be adjusted by the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch. The polymerizable liquid crystal composition may contain other polymerizable compounds in addition to the optically active compound.

  In the selective reflection of visible light, which is a characteristic of the liquid crystal film as described above, the helical structure acts on incident light and reflects circularly polarized light and elliptically polarized light. The selective reflection characteristic is expressed by λ = n · Pitch (λ is the central wavelength of selective reflection, n is the average refractive index, and Pitch is the helical pitch). By changing n or Pitch, the center wavelength (λ) and wavelength width are changed. (Δλ) can be adjusted as appropriate. In order to improve color purity, the wavelength width (Δλ) may be reduced, and when broadband reflection is desired, the wavelength width (Δλ) may be increased. Furthermore, this selective reflection is greatly influenced 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 the thickness appropriately, preferably 0.5 to 25 μm, and more preferably 1 to 10 μm.

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

  The liquid crystal film may be used for a reflective film in which the reflection wavelength region as described in JP-A-2004-333671 is set to the near infrared (wavelength 800 to 2500 nm) by making the helical pitch longer than visible light. it can. Increasing the helical pitch can be achieved by using an optically active compound with a small twisting force or by reducing the amount of optically active compound added.

  Any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. In addition, either a polymerizable compound or a non-polymerizable compound may be used, and an optimum compound can be added according to the purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is more preferable.

  Further, among the optically active compounds, those having a large twisting force (HTP: helical twisting power) are suitable for shortening the helical pitch. Representative examples of compounds having a large torsional force are disclosed in GB2298202 and DE10221751.

  The thickness (film thickness) of the liquid crystal film varies depending on the retardation corresponding to the target element and the birefringence (optical anisotropy value) of the liquid crystal film. Accordingly, the thickness range is 0.05 to 100 μm as a guide, although it varies depending on the purpose. A more preferable range is 0.1 to 50 μm, and a further preferable range is 0.5 to 20 μm. The preferred haze value of the liquid crystal film is 1.5% or less, and the preferred transmittance is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. The transmittance preferably satisfies these conditions in the visible light region.

  The liquid crystal film is effective as an optical compensation element applied to liquid crystal display elements (particularly active matrix type and passive matrix type liquid crystal display elements). Examples of types of liquid crystal display elements suitable for using this liquid crystal film as an optical compensation film are IPS type (in-plane switching), OCB type (optically compensated birefringence), TN type ( Twisted nematic), STN type (super twisted nematic), ECB type (electrically controlled birefringence), DAP type (deformation effect of aligned phase), CSH type (color super homeotropic), VAN / VAC type (vertically aligned nematic / cholesteric), OMI type (optical mode interference), SBE type (super birefringence effect), and the like. Further, the liquid crystal film can be used as a phase letter for a display element such as a guest-host type, a ferroelectric type, or an antiferroelectric type. Note that the optimum values of parameters such as the thickness distribution and thickness of the tilt angle required for the liquid crystal film strongly depend on the type of liquid crystal display element to be compensated and its optical parameters, and therefore differ depending on the type of element.

  The liquid crystal film can also be used as an optical element integrated with a polarizing plate or the like. In this case, the liquid crystal film is disposed outside the liquid crystal cell. On the other hand, since the liquid crystal film as the optical compensation element has little or no elution of impurities into the liquid crystal filled in the cell, it can be arranged inside the liquid crystal cell. For example, when the method disclosed in Japanese Patent Application Laid-Open No. 2008-01943 is applied, the function of the color filter can be further improved by forming the polymerizable liquid crystal layer of the present invention on the color filter. The homogeneously oriented liquid crystal film combined with the dichroic dye can also be used as an absorptive polarizing plate. The homogeneously oriented liquid crystal film combined with the fluorescent dye can also be used as a polarized light emitting film.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Evaluation methods in the examples are shown below.
<Polymerization conditions>
In a nitrogen atmosphere, light having an intensity of 30 mW / cm ² (365 nm) was irradiated for 30 seconds using a 250 W ultrahigh pressure mercury lamp at room temperature.
<Evaluation of homogeneous orientation>
(1) Creation of a rubbing-treated glass substrate with an alignment film A glass substrate having a thickness of 1.1 mm is spin-coated with a polyamic acid for low pretilt angle (horizontal alignment mode) (Rixon aligner: manufactured by PIA-5370 JNC). The solvent was dried on a hot plate at 80 ° C. and then baked in an oven at 230 ° C. for 30 minutes, and then rubbed using a rayon cloth.
(2) Confirmation of liquid crystal alignment uniformity Presence or absence of light leakage (transmission of fine light) when a liquid crystal film-attached substrate is placed between two polarizing plates arranged in crossed Nicols and the film is in a dark field state. Was observed. Light leakage occurs when there is a defect in the alignment of the liquid crystal. When there was no light leakage, it was judged that the orientation was uniform.
<Evaluation of homeotropic orientation>
The substrate with an alignment film described above was used as it was without rubbing treatment.
When the substrate with the liquid crystal film obtained is sandwiched between two polarizing plates arranged in crossed Nicols, the dark field is confirmed when the substrate is observed from the front, and the bright field is confirmed when observed from the top, bottom, left, and right directions. Then, in order to show that the alignment vector of the liquid crystal skeleton is perpendicular to the glass substrate, it was determined to be homeotropic alignment. The uniformity of homeotropic alignment is when the two polarizing plates are placed in a crossed Nicol state, a substrate with a liquid crystal film is inserted between them, and the light spot due to alignment defects in the liquid crystal is not visually confirmed. (Dark field) was in a uniformly oriented state.

<Measurement with ellipsometer: Confirmation of orientation form>
The substrate with a liquid crystal film was irradiated with light having a wavelength of 550 nm using an OPTIPRO ellipsometer manufactured by Shintech Co., Ltd. The retardation was measured while decreasing the incident angle of this light from 90 degrees with respect to the film surface, and the orientation form was confirmed. The direction of tilting the irradiation was matched with the rubbing direction (long axis direction of liquid crystal molecules). When the retardation from the vertical direction was the maximum, the orientation was judged to be homogeneous. In homogeneous alignment, the alignment vector of liquid crystal molecules is parallel to the support substrate. On the other hand, when the retardation from the vertical direction was the minimum, the orientation was judged to be homeotropic. In homeotropic alignment, the alignment vector of liquid crystal molecules is perpendicular to the support substrate.
Retardation (phase delay) is represented by Δn × d. Symbol Δn is refractive index anisotropy, and symbol d is the thickness (film thickness) of the polymer film.

<Film thickness measurement>
The layer of the liquid crystal film of the glass substrate with a liquid crystal film was cut out, and the step was measured using a fine shape measuring apparatus (Alphastep IQ, manufactured by KLA TENCOR Co., Ltd.).
<Evaluation of optical anisotropy (Δn)>
The retardation / film thickness was calculated from the retardation and film thickness value obtained for the liquid crystal film having homogeneous alignment.

  The compounds used in Examples and Comparative Examples are shown below.

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

(the first stage)
Trans-p-coumaric acid (2470 mmol) and concentrated sulfuric acid (10 mL) were added to methanol (1200 mL), and the mixture was stirred with heating under reflux for 5 hours. The solvent was distilled off under reduced pressure. The obtained residue was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was recrystallized with ethanol to obtain 2157 mmol of the compound (ex-1).

(Second stage)
Compound (ex-1) 561 mmol, sodium hydroxide 617 mmol and sodium iodide 56 mmol were added to 1000 mL of N, N-dimethylformamide (DMF), and the mixture was stirred at 60 ° C. in a nitrogen atmosphere. 617 mmol of 6-chlorohexanol was dripped there. After dropping, the mixture was stirred at 80 ° C. for 8 hours. The reaction solution was extracted with ethyl acetate and water. 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, 617 mmol of sodium hydroxide, was added to a mixed solution of 500 ml of water and 500 ml of methanol, and stirred for 3 hours while heating under reflux. The solvent was distilled off under reduced pressure, and the resulting residue was poured into 3N hydrochloric acid for reprecipitation. The crystals were filtered off and recrystallized from ethanol to obtain 356 mmol of compound (ex-2).

(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 acrylic acid chloride was dripped there. After dropping, the mixture was stirred at 50 ° C. for 4 hours. The reaction solution was poured into ice water, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was recrystallized from toluene to obtain 118 mmol of the compound (ex-3).

(Fourth stage)
63 mmol of compound (ex-3), 31 mmol of 9-methyl-2,7-dihydroxyfluorene and 13 mmol of 4-dimethylaminopyridine (DMAP) were added to 200 ml of dichloromethane and stirred under a nitrogen atmosphere. Thereto, 30 mL of a dichloromethane solution of 66 mmol of 1,3-dicyclohexylcarbodiimide (DCC) was dropped. After dropping, the mixture was stirred at room temperature for 8 hours. The deposited 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 obtain 20 mmol of the compound (1-1-3). The phase transition temperature of the obtained compound (1-1-3) 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), 6.16-6.09 (m, 2H), 5.83 (d, 2H), 4.18 ( t, 4H), 4.01 (t, 2H), 1.87-1.80 (m, 4H), 1.76-1.69 (m, 4H), 1.70 (m, 2H), 1 57-1.43 (m, 11H).

The compound (2-1-C3), the compound (2-1-D3) and the compound (2-1-A4) were synthesized according to the methods described in JP-A Nos. 2003-238491 and 2006-307150.
Compound (2-2-1-2) and compound (2-226-2) were synthesized according to the method described in International Publication No. 2008/136265 pamphlet.

Compound (3-4-3) was synthesized by the method described in Makromol. Chem., 190, 2255-2268 (1989). Compound (3-7-2) was synthesized according to the following method.

(the first stage)
Methylhydroquinone (322 mmol), 4-hydroxybenzoic acid (644 mmol), boric acid (10 mmol) and concentrated sulfuric acid (1 mL) were added to toluene (400 mL), and the mixture was stirred for 8 hours while dehydrating under heating and reflux using Dean-Stark. The crystals were filtered off and recrystallized with ethanol to obtain 280 mmol of the compound (ex-4).

(Second stage)
16 mmol of compound (ex-4) and 113 mmol of triethylamine were added to 40 ml of acetone, and the mixture was cooled and stirred at 5 ° C. in a nitrogen atmosphere. Thereto was added dropwise 50 mL of a toluene solution of 65 mmol of fumaric acid chloride. After dropping, the mixture was stirred at room temperature for 1 hour. Further, 20 mL of a toluene solution of 79 mmol of 4-hydroxybutyl acrylate was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 2 hours. 2N aqueous hydrochloric acid was added to the reaction solution to extract the organic layer. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then 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 obtain 6 mmol of the above compound (3-7-2). The phase transition temperature of the obtained compound (A) is as follows.
Phase transition 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), 1.89-1 .78 (m, 8H).

Compound (3-9-2) was synthesized according to the method described in US Pat. No. 5,770,107 and JP-A-2004-231638.
Compound (3-10-2) and compound (3-11-2) were synthesized according to the methods described in JP-A-2006-225607 and JP-A-2007-16213.
Compound (4-1-2) was synthesized by the method described in Macromolecules, 3938-3943, (23), 1990.
Compound (4-4-1) and compound (4-4-2) were synthesized by the method described in Makromol. Chem. 183, 2311-2321, (1982).
[Example 1]

[Preparation of polymerizable liquid crystal composition (1)]
These compounds were mixed in a weight ratio of Compound (1-1-3): Compound (2-1-A4): Compound (4-1-2) = 35: 30: 35. This composition is designated as MIX1. A polymerization initiator Irgacure Oxe01 (BASF Japan) having a weight ratio of 0.06 and a fluorine-based nonionic surfactant FTX-218 (manufactured by Neos Co., Ltd.) having a weight ratio of 0.01 were added to this MIX1. . To the composition, toluene / 2-propanol = 9/1 (weight ratio) was added to obtain a polymerizable liquid crystal composition (1) having a MIX1 of 16% by weight.

Next, a polyamic acid for low pretilt angle (horizontal alignment mode) (Rixon aligner: manufactured by PIA-5370 JNC Co.) is applied on a glass substrate (Matsunami slide glass: S-1112) and dried at 80 ° C. for 3 minutes. Then, it baked for 30 minutes at 230 degreeC, and rubbed with the rubbing cloth made from rayon. Next, the polymerizable liquid crystal composition (1) was applied by spin coating onto 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 had been removed was polymerized with ultraviolet rays in a nitrogen stream to obtain a liquid crystal film. The obtained substrate with a liquid crystal film was placed between two polarizing plates arranged in crossed Nicols, and when the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and the orientation was judged to be uniform. When the retardation of the substrate with a liquid crystal film was measured, the result was as shown in FIG. 1. Since the retardation from the vertical direction was the maximum, it was judged that the orientation was homogeneous. Further, the retardation measurement value at 90 degrees with respect to the film surface was 135 nm, and the film thickness was 563 nm, so Δn was calculated to be 0.24.
[Comparative Example 1]

化合物（３−４−３）：化合物（４−１−２）：化合物（β）＝４０：３５：２５の重量比でこれらの化合物を混合したこと以外は実施例１と同様にして化合物を混合した。この組成物をＭＩＸ２とする。このＭＩＸ２を用いたこと以外は実施例１と同様にして重合性液晶組成物（２）を調製し、液晶フィルムを形成したところ、実施例１と同様なホモジニアス配向が得られたが、実施例１と同様にしてΔｎを算出したところ０．１５であり、大きな屈折率異方性にならなかった。 The following compound (β) was synthesized by the method described in JP-A-2006-111571.

Compound (3-4-3): Compound (4-1-2): Compound (β): The compound was prepared in the same manner as in Example 1 except that these compounds were mixed at a weight ratio of 40:35:25. Mixed. This composition is designated as MIX2. A polymerizable liquid crystal composition (2) was prepared in the same manner as in Example 1 except that this MIX2 was used, and a liquid crystal film was formed. As a result, the same homogeneous alignment as in Example 1 was obtained. When Δn was calculated in the same manner as in 1, it was 0.15, and the refractive index anisotropy was not large.

From the above results, it can be seen that a large refractive index anisotropy can be easily obtained by using the compounds (1) and (2).
[Example 2]

  MIX1 described in Example 1 is a compound having a weight ratio of 0.10 (α-2), a 3-aminopropyltriethoxysilane having a weight ratio of 0.10 (manufactured by JNC Corporation, trade name: Silaace S-330) and a weight ratio. 0.03 polymerization initiator Irgacure Oxe01 (manufactured by BASF Japan) was mixed, toluene / 2-propanol = 9/1 (weight ratio) was added, and a polymerizable liquid crystal composition (3) with MIX1 of 20% by weight (3 ) Was prepared.

A polyamic acid (Rixon aligner: manufactured by PIA-5370 JNC) for low pretilt angle (horizontal alignment mode) is applied on a glass substrate (Matsunami slide glass: S-1112), dried at 80 ° C. for 3 minutes, and then 230. What was baked for 30 minutes at ° C. was used as a substrate for evaluation. Then, the polymerizable liquid crystal composition (3) was applied onto a glass substrate with a polyamic acid film by spin coating. 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 had been removed was polymerized with ultraviolet rays in a nitrogen stream to obtain a liquid crystal film. The obtained substrate with a liquid crystal film was placed between two polarizing plates arranged in crossed Nicols, and when the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and the orientation was judged to be uniform. When the retardation of the substrate with a liquid crystal film was measured, the result was as shown in FIG. 2. Since the retardation from the vertical direction was the smallest, the orientation was determined to be homeotropic. The measured retardation value at 45 degrees with respect to the film surface 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 described in Comparative Example 1 was used to obtain a liquid crystal film. The obtained substrate with a liquid crystal film was placed between two polarizing plates arranged in crossed Nicols, and when the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and the orientation was judged to be uniform. When the retardation of the substrate with a liquid crystal film was measured, the result was as shown in FIG. 2. Since the retardation from the vertical direction was the smallest, the orientation was determined to be homeotropic. Further, the measured retardation value at 45 degrees with respect to the film surface was 37 nm, and the film thickness was about 1.6 μm. From this, it can be seen that when the compounds (1) and (2) are used, a large retardation of a homeotropically aligned liquid crystal film can be obtained.
[Example 3]

Compound (1-1-3): Compound (2-1-D3): These compounds were mixed at a weight ratio of 70:30 to form MIX3, and the solvent was cyclopentanone / propylene glycol monomethyl ether acetate (PGMEA) = A polymerizable liquid crystal composition (5) was prepared in the same manner as in Example 1 except that MIX3 was 16% by weight as 9/1 (weight ratio). And when the liquid crystal film was formed by the same method as Example 1, the liquid crystal film which has uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as in FIG. 1, and Δn calculated was 0.23.
[Example 4]

Compound (1-1-3): Compound (2-1-D3): Compound (4-1-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 60:20:20. A polymerizable liquid crystal composition (6) was prepared in the same manner as described above, and a liquid crystal film was formed. As a result, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as in FIG. 1, and Δn calculated was 0.23.
[Example 5]

Compound (1-1-3): Compound (2-1-A4): Compound (2-1-D3) As described in Example 1, except that these compounds were mixed at a weight ratio of 60:20:20. A polymerizable liquid crystal composition (7) was prepared in the same manner as described above, and a liquid crystal film was formed. As a result, a liquid crystal film having uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 6]

A polymerizable liquid crystal composition (in the same manner as in Example 1 except that these compounds were mixed at a weight ratio of Compound (1-1-3): Compound (2-1-A4) = 70: 30. 8) was prepared and a liquid crystal film was formed to obtain a liquid crystal film having uniform homogeneous alignment. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.26.
[Example 7]

Compound (1-1-3): Compound (2-1-A4) = polymerizable liquid crystal composition (in the same manner as in Example 1 except that these compounds were mixed at a weight ratio of 50:50) 9) was prepared and a liquid crystal film was formed to obtain a liquid crystal film having uniform homogeneous alignment. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 8]

Polymerizable liquid crystal composition in the same manner as in Example 1 except that these compounds were mixed in a weight ratio of compound (1-1-3): compound (2-26-2-2) = 50: 50. When the product (10) was prepared and a liquid crystal film was formed, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.20.
[Example 9]

Compound (1-1-3): Compound (2-1-C-3) = Polymerizable liquid crystal composition in the same manner as in Example 1 except that these compounds were mixed at a weight ratio of 50:50. When product (11) was prepared and a liquid crystal film was formed, a liquid crystal film having uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 10]

Compound (1-1-3): Compound (2-2-1-2) = polymerizable liquid crystal composition in the same manner as described in Example 1, except that these compounds were mixed at a weight ratio of 50:50. When the product (12) was prepared and a liquid crystal film was formed, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.22.
[Example 11]

Compound (1-1-3): Compound (2-1-A4): Compound (4-1-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 50:25:25. A polymerizable liquid crystal composition (13) was prepared in the same manner as described above, and a liquid crystal film was formed. As a result, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 12]

Compound (1-1-3): Compound (2-1-A4): Compound (2-1-C3): Compound (4-1-2) = These compounds in a weight ratio of 50: 20: 10: 20 A polymerizable liquid crystal composition (14) was prepared in the same manner as in Example 1 except that was mixed, and a liquid crystal film was formed to obtain a liquid crystal film having uniform homogeneous alignment. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.20.
[Example 13]

Compound (1-1-3): Compound (2-1-A4): Compound (4-4-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 50:20:30. A polymerizable liquid crystal composition (15) was prepared in the same manner as described above, and when a liquid crystal film was formed, a liquid crystal film having uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as in FIG. 1, and Δn calculated was 0.23.
[Example 14]

Compound (1-1-3): Compound (2-1-A4): Compound (4-4-1) = 50:25:25 As described in Example 1, except that these compounds were mixed in a weight ratio. A polymerizable liquid crystal composition (16) was prepared in the same manner as described above, and when a liquid crystal film was formed, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 15]

Compound (1-1-3): Compound (2-1-A4): Compound (3-11-2) = The compound described in Example 1 except that these compounds were mixed at a weight ratio of 30:20:50. A polymerizable liquid crystal composition (17) was prepared in the same manner as in the method, and a liquid crystal film was formed to obtain a liquid crystal film having uniform homogeneous alignment. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.26.
[Example 16]

Compound (1-1-3): Compound (2-1-A4): Compound (3-10-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 30:20:50. A polymerizable liquid crystal composition (18) was prepared in the same manner as described above, and when a liquid crystal film was formed, a liquid crystal film having uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as FIG. 1, and Δn was 0.24.
[Example 17]

Compound (1-1-3): Compound (2-1-A4): Compound (3-9-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 30:20:50. A polymerizable liquid crystal composition (19) was prepared in the same manner as described above, and when a liquid crystal film was formed, a liquid crystal film having uniform homogeneous alignment was obtained. When the retardation of this film was measured, it was the same result as in FIG. 1, and Δn calculated was 0.23.
[Example 18]

Compound (1-1-3): Compound (2-1-A4): Compound (3-7-2) = As described in Example 1, except that these compounds were mixed at a weight ratio of 30:20:50. A polymerizable liquid crystal composition (20) was prepared in the same manner as described above, and when a liquid crystal film was formed, a liquid crystal film having uniform homogeneous orientation was obtained. When the retardation of this film was measured, it was the same result as in FIG. 1, and Δn calculated was 0.23.
[Example 19]

  Compound (1-1-3): Compound (2-1-A4): Compound (3-11-2): Compound (4-1-2) = These compounds at a weight ratio of 40: 20: 20: 20 A polymerizable liquid crystal composition (21) was prepared in the same manner as in Example 1 except that was mixed, and a liquid crystal film was formed to obtain a liquid crystal film having uniform homogeneous alignment. When the retardation of this film was measured, it was the same result as FIG. 1, and it was 0.25 when (DELTA) n was computed.

  By using the polymerizable liquid crystal composition of the present invention, a liquid crystal film having a uniform homogeneous alignment form or homeotropic alignment form can be obtained, and the obtained liquid crystal film has a relatively large refractive index anisotropy.

Claims (5)

At least selected from the group of at least one compound selected from the group of compounds represented by formula (1) (A) component, the equation (2-1) to (2-2) and a compound represented by is one compound component (B) contains at least one is a compound (C) component, and a nonionic surfactant selected from the group of compounds represented by formula (3), (a) In a ratio based on the total weight of the component to the component (C), the component (A) is 1 to 99% by weight, the component (B) is 1 to 99% by weight, and the component (C) is 1 to 98%. wt% der Ru polymerizable liquid crystal composition.

In 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 carbons or alkoxy having 1 to 7 carbons;
X ¹ is independently hydrogen, methyl or trifluoromethyl;
Y ¹ is independently alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — may be —O—, —S—, —COO. -, -OCO-, -OCOO-, -CH = CH-, or -C≡C- may be substituted.

In 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, cyano or alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons;
n ^2A is independently an integer from 2 to 10;
Z ^21A is independently a single bond, —CH ₂ CH ₂ —;
In 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 a -C≡C-;
Z ^22B is independently a single bond or —O—;
A ²¹ 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, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trimethyl May be replaced by fluoroacetyl, difluoromethyl or trifluoromethyl;
Y ^2B is independently an alkylene having 2 to 20 carbon atoms, and in this alkylene, any hydrogen may be replaced by fluorine or chlorine, and any —CH ₂ — may be —O—, —COO—, —OCO. -, -CH = CH- or -C≡C- may be substituted.

In equation (3),
X ³ is independently hydrogen, methyl or trifluoromethyl;
W ³¹ is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine;
r is an integer from 0 to 4;
W ³² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 7 carbons or alkoxy having 1 to 7 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced with 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—. In formula (1) according to claim 1,
W ¹¹ is independently hydrogen, methyl or ethyl;
W ¹² is independently hydrogen, fluorine, chlorine, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons;
X ¹ is independently hydrogen or methyl;
Y ¹ is independently alkylene having 1 to 12 carbons, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO May be replaced by-, -OCOO-, -CH = CH- or -C≡C-;
In the formula (2-1) according to claim 1,
X ^2A is independently hydrogen or methyl;
W ^21A is independently hydrogen, methyl or ethyl;
W ^22A is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons;
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) according to claim 1,
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 a -C≡C-;
Z ^22B is independently a single bond or —O—;
A ²¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-phenylene, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl. Any hydrogen in phenylene and 1,4-phenylene may be replaced by fluorine, chlorine, cyano, methyl, ethyl, methoxy, difluoromethyl or trifluoromethyl;
Y ^2B is independently alkylene having 2 to 10 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is —O—, —COO—, —OCO -, - rather than good be replaced by CH = CH- or -C≡C-,
In formula (3) according to claim 1,
X ³ is independently hydrogen or methyl;
W ³¹ is independently hydrogen, fluorine, chlorine, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine ;
r is an integer from 0 to 2;
W ³² is independently hydrogen, halogen, nitro, cyano, alkyl having 1 to 3 carbons or alkoxy having 1 to 3 carbons, and in this alkyl and alkoxy, any hydrogen may be replaced by fluorine;
n ³¹ is independently an integer from 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- der is,
The nonionic surfactant is a fluorine-based, silicone-based or hydrocarbon-based nonionic surfactant,
The ratio based on the total weight of the component (A) to the component (C), the component (A) is 3 to 95% by weight, the component (B) is 3 to 95% by weight, and the component (C) is 1-94 wt% der Ru, polymerizable liquid crystal composition according to claim 1. In formula (1) according to claim 1,
W ¹¹ is independently hydrogen or methyl;
W ¹² is independently hydrogen, fluorine, chlorine, methyl or methoxy;
X ¹ is independently hydrogen or methyl;
Y ¹ is independently alkylene having 1 to 10 carbon atoms, and in this alkylene, any —CH ₂ — is —O—, —COO—, —OCO—, —OCOO—, —CH═CH— or —C May be replaced by ≡C-;
In the formula (2-1) according to claim 1,
X ^2A is independently hydrogen or methyl;
W ^21A is 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) according to claim 1,
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 a -C≡C-;
Z ^22B is independently a single bond or —O—;
A ²¹ is independently 1,4-cyclohexylene, 1,4-phenylene or 1,3-phenylene, and in this 1,3-phenylene and 1,4-phenylene, any hydrogen is fluorine, methyl, May be replaced by methoxy or trifluoromethyl;
Y ^2B is independently alkylene having 2 to 10 carbon atoms, and in this alkylene, arbitrary hydrogen may be replaced by fluorine, and arbitrary —CH ₂ — represents —O—, —COO—, —OCO—, -CH = CH- or -C≡C- may be substituted,
In formula (3) according to claim 1,
X ³ is independently hydrogen or methyl;
W ³¹ is independently hydrogen, fluorine, cyano, methyl or methoxy, in which any hydrogen may be replaced by fluorine;
r is an integer from 0 to 2;
W ³² is independently hydrogen, fluorine, cyano, methyl or methoxy, in which any hydrogen may be replaced by fluorine;
n ³¹ is independently an integer from 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- der is,
The nonionic surfactant is a fluorine-based, silicone-based or hydrocarbon-based nonionic surfactant, and is a ratio based on the total weight of the components (A) to (C). a 5 to 90% by weight, (B) component is from 5 to 90 wt%, (C) component Ru 1 to 90 wt% der polymerizable liquid crystal composition according to claim 1. Polymerizable optically anisotropic medium obtained by polymerizing at least one liquid crystal composition according to any one of claims 1-3. A liquid crystal display element having the optical anisotropic body according to claim 4 .

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