JP2006307150A - Polymerizable liquid crystal composition and optically anisotropic thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically anisotropic thin film which is reduced in the change of optical properties even when it is heated at 200°C, and to provide a polymerizable liquid crystal composition as a raw material of the film. <P>SOLUTION: The polymerizable liquid composition contains compounds expressed by formulae (1-12) and (2-5). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymerizable liquid crystal composition containing an acrylate derivative having a 9,9-dialkylfluorene skeleton, a polymerizable liquid crystal layer and a liquid crystal thin film obtained from the composition. Furthermore, the present invention relates to an optical element using this thin film, a polarizing plate, a retardation film, a display device having these, and the like.

  In recent years, applications to optical elements such as polarizing plates and retardation plates using liquid crystals having a polymerizable group have been proposed. These optical elements are obtained by polymerizing a polymerizable liquid crystal having optical anisotropy in a liquid crystal state and fixing the state. The polymerizable liquid crystal can be polymerized while maintaining the alignment state after appropriate alignment control in the liquid crystal state. Therefore, a polymer having various optical anisotropies can be obtained by fixing the alignment state of the liquid crystal skeleton in an alignment state such as homogeneous alignment, hybrid alignment, homeotropic alignment, or twist alignment. In the following description, the above-described orientation state may be simplified and described as “having homogeneous orientation”, “having hybrid orientation”, “having homeotropic orientation”, or “having twist orientation” .

The polymer having homogeneous orientation can be used in combination with, for example, a ½ wavelength plate, a ¼ wavelength plate, or a film having other optical functions (see Patent Document 1). A polymer having a hybrid orientation can be applied to, for example, a viewing angle compensator in a TN (Twisted Nematic) mode (see Patent Documents 2 to 5). A polymer having homeotropic alignment can improve viewing angle characteristics of a polarizing plate by combining with a film having other optical functions, for example. Polymers having homeotropic orientation are classified as positive C-plates in the refractive index ellipsoid because the optical axis direction is in the _nz direction and the refractive index in the optical axis direction is greater than the refractive index in the orthogonal direction. Is done. This positive C-plate is used in combination with a film having other optical functions for optical compensation such as a horizontally aligned liquid crystal display mode, so-called IPS (In-Plane Switching) mode, for example, for improving the viewing angle characteristics of a polarizing plate. (See Patent Document 6).

  For any of the above applications, a liquid crystal thin film having optical anisotropy can be provided inside the liquid crystal cell, or can be provided outside the liquid crystal cell. An example of a method of providing a liquid crystal thin film inside a liquid crystal cell is described in Patent Document 7. An example of a system in which a liquid crystal thin film is provided outside a liquid crystal cell is described in Patent Document 8. In the case of the external method, the polymerizable liquid crystal composition may be applied on a film made of a polymer such as TAC (triacetyl cellulose) or norbornenes as a substrate.

  When a liquid crystal thin film having optical anisotropy is provided in a liquid crystal cell by polymerizing the polymerizable liquid crystal composition, the following characteristics are required for the polymerizable liquid crystal composition. Examples of characteristics before polymerization include having a nematic phase stable at room temperature, showing uniform orientation, and easily achieving various desired orientation forms. Examples of the characteristics after polymerization are good adhesion to the substrate, characteristic values (such as retardation) representing appropriate optical anisotropy according to the optical design, and transparency. And the weather resistance (heat resistance, moisture resistance, light resistance etc.) which does not change these characteristics is calculated | required. Especially when it is provided inside the cell, a liquid crystal thin film is formed on the substrate and an overcoat, a transparent electrode and an alignment film for driving liquid crystal are formed. In order to counteract the above, heat resistance is required in which the adhesiveness to each layer of the liquid crystal thin film, the characteristic value representing the optical anisotropy, the film thickness, and the transparency do not change beyond the allowable range.

As a polymerizable liquid crystal composition for realizing the above contents, a polymerizable liquid crystal composition containing an acrylate derivative having a 9-monoalkylfluorene skeleton has been proposed (see Patent Document 9). However, an acrylate derivative having a 9-monoalkylfluorene skeleton has a chemically unstable structure, and particularly in the production of a liquid crystal display device in which a liquid crystal thin film is provided inside a liquid crystal cell, on a liquid crystal film formed on a substrate, Due to thermal history when forming overcoat, transparent electrode and alignment film for driving liquid crystal, characteristic value indicating optical anisotropy changes, film thickness decreases significantly, thin film changes color (yellowing) and is transparent Improvements have been desired since problems such as deterioration of properties occur.
JP 2002-372623 A JP 2002-122741 A JP 2002-207121 A JP 2002-207125 A Japanese Patent Laid-Open No. 2002-243942 JP 2004-198478 A Japanese Patent Laid-Open No. 2002-222009 JP 2001-372623 A JP 2004-204190 A Y. Hisatake et al, Asia Display / IDW '01 LCT8-2

  An object of the present invention is, for example, to obtain a liquid crystal thin film with little change in optical properties under heating conditions of 200 ° C. when a polymerizable liquid crystal composition is polymerized to obtain a liquid crystal thin film having optical anisotropy. It is. In particular, it is to provide a polymerizable liquid crystal composition capable of forming an optically anisotropic liquid crystal thin film layer inside a liquid crystal cell. An object of the present invention is to provide a polymerizable liquid crystal composition in which the alignment state of the liquid crystal skeleton in the liquid crystal thin film is homogeneous alignment, hybrid alignment, or homeotropic alignment. Furthermore, an object of the present invention is to provide a liquid crystal thin film and an optical element using the thin film. It is also an object of the present invention to provide a display device including an optical element using the liquid crystal thin film, particularly a liquid crystal display device.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using an acrylate derivative having a 9,9-dialkylfluorene skeleton as the main component of the polymerizable liquid crystal composition. The present invention has been reached. The first item of the present invention is the following item [1].

ここに、Ｒは炭素数１〜４のアルキルであり；Ｗ^１およびＷ^２は独立して水素、塩素、フッ素または−ＣＨ_３であり；Ｗ^３およびＷ^４は独立して水素、塩素、フッ素、−ＣＨ_３または−ＣＦ_３であり；Ｗ^５は炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、塩素、フッ素、−ＣＮまたは−ＯＣＦ_３であり；Ｘは単結合、−ＣＨ＝ＣＨ−または−ＣＨ_２ＣＨ_２−であり；Ｚは単結合、−ＣＯＯ−、−ＯＣＯ−または−ＣＨ_２ＣＨ_２−であり；そしてｑは１〜２０の整数である。 [1] A composition comprising a compound represented by formula (1) and at least one of a compound represented by formula (2) and a compound represented by formula (3), wherein the formula (1) The proportion of the compound represented by formula (1) is 50 to 99% by weight based on the total amount of the compound represented by formula (2), the compound represented by formula (2) and the compound represented by formula (3). A polymerizable liquid crystal composition in which the proportion of the compound represented by the formula (2) is 0 to 50% by weight and the proportion of the compound represented by the formula (3) is 0 to 50% by weight:

Where R is alkyl having 1 to 4 carbon atoms; W ¹ and W ² are independently hydrogen, chlorine, fluorine or —CH ₃ ; W ³ and W ⁴ are independently hydrogen, chlorine, fluorine , —CH ₃ or —CF ₃ ; W ⁵ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, chlorine, fluorine, —CN or —OCF ₃ ; X is a single bond, —CH 3 ═CH— or —CH ₂ CH ₂ —; Z is a single bond, —COO—, —OCO— or —CH ₂ CH ₂ —; and q is an integer of 1-20.

  The polymerizable liquid crystal composition of the present invention has, for example, characteristics such as excellent stability of the liquid crystal phase at room temperature, uniform alignment before and after polymerization, and optically anisotropic liquid crystal layer. Alternatively, a liquid crystal thin film can be obtained. This optically anisotropic liquid crystal thin film has excellent heat resistance. This heat resistance makes it possible to form an optically anisotropic liquid crystal thin film layer inside the liquid crystal cell. From the polymerizable liquid crystal composition of the present invention, a liquid crystal film in which the alignment state of the liquid crystal skeleton is homogeneous alignment, hybrid alignment, or homeotropic alignment can be obtained. The liquid crystal thin film of the present invention can be applied to various optical elements, and this optical element can be applied to a display device, particularly a liquid crystal display device.

  Terms used in the present invention will be described. The angle formed by the alignment state of the liquid crystal skeleton with the substrate plane is defined as a “tilt angle”. An alignment state in which the tilt angle is uniformly close to zero from one interface to the other interface and in particular is 0 to 5 ° is referred to as “homogeneous alignment”. Here, the interface is a substrate interface provided with an alignment layer or a free interface. An alignment state in which the tilt angle continuously changes in the range of 0 to 90 ° is referred to as “hybrid alignment”. An alignment state in which the tilt angle is uniformly 85 to 90 ° from one interface to the other interface is referred to as “homeotropic alignment”. The compound represented by formula (1) may be referred to as compound (1). The compounds represented by other formulas may be similarly described. The symbol -CN means -C≡N (cyano group).

ここに、Ｗ^２は水素またはフッ素であり；そしてｑは２〜１０の整数である。 The present invention comprises the above item [1] and the following items [2] to [23].
[2] A composition comprising a compound represented by formula (4) and at least one of a compound represented by formula (5) and a compound represented by formula (6), wherein the formula (4) The proportion of the compound represented by formula (4) is 50 to 90% by weight based on the total amount of the compound represented by formula (5), the compound represented by formula (5) and the compound represented by formula (6). The proportion of the compound represented by formula (5) is 0 to 50% by weight, the proportion of the compound represented by formula (6) is 0 to 50% by weight, and represented by formula (5). A polymerizable liquid crystal composition in which the total of the proportion of the compound and the proportion of the compound represented by formula (6) is 10 to 50% by weight:

Where W ² is hydrogen or fluorine; and q is an integer from 2 to 10.

[3] The ratio of the compound represented by the formula (4) is 50 to 90% by weight, the ratio of the compound represented by the formula (5) is 10 to 50% by weight, and the formula (6) The polymerizable liquid crystal composition according to item [2], wherein the proportion of the compound to be produced is 0% by weight.

[4] The ratio of the compound represented by the formula (4) is 50 to 90% by weight, the ratio of the compound represented by the formula (5) is 0% by weight, and the compound represented by the formula (6) The polymerizable liquid crystal composition according to the item [2], wherein the ratio of is 10 to 50% by weight.

[5] The proportion of the compound represented by the formula (4) is 50 to 80% by weight, the proportion of the compound represented by the formula (5) is 10 to 40% by weight, and is represented by the formula (6). The ratio of the compound is 10 to 40% by weight, and the sum of the ratio of the compound represented by the formula (5) and the ratio of the compound represented by the formula (6) is 20 to 50% by weight. 2. The polymerizable liquid crystal composition according to 2.

[6] The proportion of the compound represented by the formula (4) is 50 to 80% by weight, the proportion of the compound represented by the formula (5) is 10 to 40% by weight, and is represented by the formula (6). And the total of the proportion of the compound represented by the formula (5) and the proportion of the compound represented by the formula (6) is 20 to 50 wt%, and W ² The polymerizable liquid crystal composition according to item [2], wherein is hydrogen.

ここに、Ｒ^２は水素または炭素数１〜８のアルキルであり；Ｒ^３は炭素数１〜８のアルキルであり；Ｙは炭素数１〜２０のアルキレンであり；そしてｎは０〜２の整数である。 [7] A composition further containing a compound represented by formula (7), wherein the ratio of the compound represented by formula (7) is 1 to 20% by weight based on the total amount of the composition. ] The polymerizable liquid crystal composition according to any one of items [6] to [6].

Where R ² is hydrogen or alkyl having 1 to 8 carbon atoms; R ³ is alkyl having 1 to 8 carbon atoms; Y is alkylene having 1 to 20 carbon atoms; and n is 0 to 2 It is an integer.

[8] In the formula (7), Y is trimethylene, R ³ is ethyl, and n is 0; and the proportion of the compound represented by the formula (7) is 1 to 10% by weight. The polymerizable liquid crystal composition according to item 7].

[9] A polymerizable liquid crystal layer formed by applying the polymerizable liquid crystal composition according to any one of [1] to [8] onto a glass substrate.

[10] The polymerizable liquid crystal layer according to the item [9], wherein the glass substrate is a surface-treated glass substrate.

[11] The polymerizable liquid crystal layer according to the item [10], wherein the surface-treated glass substrate is a glass substrate obtained by providing a polyimide alignment film on the surface and rubbing it.

[12] It is formed by applying the polymerizable liquid crystal composition according to any one of [3] to [5] on a glass substrate on which a polyimide alignment film is provided on a surface and rubbed, and the alignment state A polymerizable liquid crystal layer having a homogeneous orientation.

[13] A polymerizable liquid crystal formed by coating the polymerizable liquid crystal composition according to the item [6] on a glass substrate on which a polyimide alignment film is provided and rubbed, and the alignment state is hybrid alignment layer.

[14] A polymerizable liquid crystal layer formed by applying the polymerizable liquid crystal composition according to the item [7] or [8] onto a glass substrate and having an orientation state of homeotropic alignment.

[15] An optically anisotropic liquid crystal thin film having a fixed orientation, obtained by polymerizing the polymerizable liquid crystal layer according to any one of [12] to [14].

[16] The optically anisotropic liquid crystal thin film according to item [15], having a thickness of 0.05 to 5 μm.

[17] An optical element having the optically anisotropic liquid crystal thin film according to the item [15].

[18] A retardation plate having the optically anisotropic liquid crystal thin film according to the item [15].

[19] A polarizing plate having the optically anisotropic liquid crystal thin film according to the item [15].

[20] An optical element having the retardation plate according to the item [18] or the polarizing plate according to the item [19].

[21] A display device having the retardation plate according to item [18] or the polarizing plate according to item [19].

[22] A liquid crystal display device comprising the retardation plate according to the item [18] or the polarizing plate according to the item [19].

[23] A liquid crystal display device in which the optically anisotropic liquid crystal thin film according to the item [15] is formed on an inner surface of a liquid crystal cell.

これらの式における記号の意味は前記の通りである。 The liquid crystal composition of the present invention is a composition containing compound (1) and at least one of compound (2) and compound (3).

The meanings of the symbols in these formulas are as described above.

式（４）において、Ｗ^２は水素またはフッ素であり、そしてｑは２〜１０の整数である。化合物（４）は液晶相の温度範囲が広いので、組成物の液晶温度範囲を調製する目的に使用する。そして、化合物（４）は他の重合性液晶化合物との相溶性に優れているので、これを用いて好適に重合性液晶組成物を調製することができる。化合物（１）の好ましい例を次に示す。 R in Formula (1) is alkyl having 1 to 4 carbons. Preferred examples of R are methyl and ethyl, with methyl being most preferred. A preferred example of compound (1) is compound (4).

In the formula (4), W ² is hydrogen or fluorine, and q is an integer of 2 to 10. Since compound (4) has a wide liquid crystal phase temperature range, it is used for the purpose of adjusting the liquid crystal temperature range of the composition. And since a compound (4) is excellent in compatibility with another polymeric liquid crystal compound, a polymeric liquid crystal composition can be suitably prepared using this. Preferred examples of compound (1) are shown below.

式（５）におけるｑは２〜１０の整数である。化合物（５）は重合性液晶組成物の配向を安定化させる目的で使用する。重合性液晶組成物に加えることで、配向欠陥を少なくすることができる。化合物（５）は液晶相を示す化合物でなくてもよい。化合物（５）の好ましい例を次に示す。

A preferred example of compound (2) is compound (5).

Q in Formula (5) is an integer of 2-10. The compound (5) is used for the purpose of stabilizing the alignment of the polymerizable liquid crystal composition. By adding to the polymerizable liquid crystal composition, alignment defects can be reduced. Compound (5) may not be a compound showing a liquid crystal phase. Preferred examples of compound (5) are shown below.

In addition to the example of the above compound (5), the following compounds can also be mentioned as preferred examples of the compound (2).

式（６）におけるｑは２〜１０の整数である。化合物（６）は重合性液晶組成物の融点を調整する目的で使用する。この化合物を重合性液晶組成物に加えることにより、組成物の融点を室温付近に調整することができる。化合物（６）の好ましい例を次に示す。

A preferred example of compound (3) is compound (6) having a cyano group at the terminal.

Q in Formula (6) is an integer of 2-10. Compound (6) is used for the purpose of adjusting the melting point of the polymerizable liquid crystal composition. By adding this compound to the polymerizable liquid crystal composition, the melting point of the composition can be adjusted to around room temperature. Preferred examples of compound (6) are shown below.

  Next, the ratio of each component constituting the polymerizable liquid crystal composition of the present invention will be described. The proportion of the compound (1) as the main component is 50 to 99 weight percent based on the total amount of the compound (1), the compound (2) and the compound (3), and the preferred range is 50 to 90% by weight. is there. One or both of compound (2) and compound (3) are used. The ratio of these compounds is 0 to 50 weight percent, respectively, based on the total amount of the compounds (1) to (3). The preferred range of this proportion is 0 or 10 to 50% by weight. The more preferable range in the case of using a compound (2) and a compound (3) together is 10 to 40 weight%, respectively. In addition, as for any of a compound (1) -compound (3), only one compound may be used and it may use it in combination of a some compound.

これらの式における記号の意味は前記の通りである。 A preferred example of the composition of the present invention is a composition containing compound (4) and at least one of compound (5) and compound (6). At this time, the ratio of the compound (4) is 50 to 90% by weight and the ratio of the compound (5) is 0 to 50% based on the total amount of the compound (4), the compound (5) and the compound (6). The ratio of the compound (6) is 0 to 50% by weight, and the total of the ratio of the compound (5) and the ratio of the compound (6) is 10 to 50% by weight.

The meanings of the symbols in these formulas are as described above.

One of the more preferable examples of the preferable composition is that the ratio of the compound (4) is 50 to 80% by weight, the ratio of the compound (5) is 10 to 40% by weight, and the ratio of the compound (6). Is 10 to 40% by weight, and the total of the proportion of the compound (5) and the proportion of the compound (6) is 20 to 50% by weight. In the following description, this composition may be referred to as composition A. At this time, a composition using the compound (4) in which W ² is hydrogen is more preferable.

  Another more preferable example of the composition of the present invention is that the proportion of the compound (4) is 50 to 90% by weight, the proportion of the compound (5) is 10 to 50% by weight, It is a composition whose ratio is 0% by weight. In the following description, this composition may be referred to as composition B.

  Yet another more preferred example of the composition of the present invention is that the proportion of compound (4) is 50 to 90% by weight, the proportion of compound (5) is 0% by weight, and It is a composition whose ratio is 10 to 50% by weight. In the following description, this composition may be referred to as composition C.

この式における記号の意味は前記の通りである。そして、式（７）においてＲ^３がエチルであり、Ｙがトリメチレンであり、そしてｎが０である下記の化合物が特に好ましい。

The polymerizable liquid crystal composition of the present invention can further contain an organosilicon compound having a primary amino group. Such a polymerizable liquid crystal composition has a characteristic that it easily develops homeotropic alignment. A specific example of the organosilicon compound having a primary amino group is a compound represented by the above formula (7). When the compound (7) is used, the preferable ratio is 1 to 20% by weight based on the total amount of the compounds (1) to (3) and the compound (7), and the more preferable ratio is 1 to 10% by weight. It is.

The meanings of the symbols in this formula are as described above. And the following compounds in which R ³ is ethyl in formula (7), Y is trimethylene, and n is 0 are particularly preferable.

  A composition containing compound (1), compound (2) and compound (3) and a composition containing compound (1) and compound (2) and not containing compound (3) are all on the glass substrate. When a polyimide alignment film is provided, and this is rubbed and then coated thereon to form a polymerizable liquid crystal layer, homogeneous alignment is achieved. Preferred examples of these compositions are Composition A and Composition B. A composition containing the compound (1) and the compound (3) and not containing the compound (2) is hybrid-aligned when a polymerizable liquid crystal layer is formed in the same manner. A preferred example of this composition is Composition C. Compound (7) is added to a composition containing compound (1), compound (2) and compound (3) or a composition containing compound (1) and compound (2) and not containing compound (3). A composition in which the ratio of the compound (7) is 1 to 20% by weight based on the total amount of the compound (1) to the compound (3) and the compound (7) is coated on a glass substrate to form a polymerizable liquid crystal layer. When formed, homeotropic orientation occurs. At this time, a polyimide alignment film may not be provided on the glass substrate. A preferred example of such a composition is a composition obtained by adding the compound (7) to the composition A or the composition B, and the ratio of the compound (7) in these examples is from the compound (4) to the compound (6 ) And compound (7) based on the total amount of 1 to 10% by weight.

  The optically anisotropic thin film obtained by polymerizing the polymerizable liquid crystal composition of the present invention on a substrate does not turn yellow even under the condition of being heated to 200 ° C., has a small decrease in retardation, and a decrease in film thickness. It has few features, such as being transparent and not peeling from the substrate. That is, it has heat resistance enough to withstand the annealing in the deposition of transparent electrodes and the formation of polyimide-based alignment films. Therefore, it can be suitably used for a liquid crystal display device in which a liquid crystal thin film is provided inside the liquid crystal cell.

  The preferred film thickness of the optically anisotropic thin film of the present invention is 0.01 to 10 μm. A more preferable range of this film thickness is 0.05 to 5 μm.

  In the polymerizable liquid crystal composition of the present invention, a polymerizable compound other than the above polymerizable liquid crystal compound can be blended within a range not impairing the effects of the invention. This polymerizable compound may not be liquid crystalline. The preferred amount of the non-liquid crystalline polymerizable compound varies depending on the structure of the polymerizable liquid crystal compound and the composition ratio thereof, but is usually 40% by weight or less based on the total amount of the composition. A more preferred range is 30% by weight or less, and a further preferred range is 20% by weight or less. In order that the liquid crystallinity of the composition is maintained and the liquid crystal layer is not separated, this ratio is preferably 40% by weight or less. Examples of polymerizable compounds that are not liquid crystalline are polyester (meth) acrylates, polyurethane (meth) acrylates, epoxy resins, and the like. The polyester (meth) acrylate is obtained by reacting (meth) acrylic acid with a polyester prepolymer of a polyhydric alcohol and a monobasic acid or a polybasic acid. The polyurethane (meth) acrylate is obtained by reacting a polyol and a compound having two isocyanate groups and then reacting with (meth) acrylic acid. Examples of epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, fatty acid type epoxy resin, alicyclic type epoxy resin, amine epoxy resin , Triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin and the like. In addition, (meth) acrylate is a general term for acrylate and methacrylate, and meth) acrylic acid is a general term for acrylic acid and methacrylic acid.

  Preferred examples of the non-liquid crystalline polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, vinyl chloride, and vinyl fluoride. , Vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2- Vinyl methylbutanoate, N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, styrene, o-, m- or p-chloromethylstyrene, α-methylstyrene , Ethyl vinyl ether, hydroxybutyl monovinyl ether, t- Mill vinyl ether, cyclohexanedimethanol vinyl ether, tetrafluoroethylene, and hexafluoropropene.

  In order to further increase the film-forming ability of the polymer, a polyfunctional acrylate can be added to the composition. Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl di Acrylate, and polyethylene glycol diacrylate.

  In order to optimize the polymerization rate of the polymerizable liquid crystal composition, a known photopolymerization initiator may be used. A preferable addition amount of the photopolymerization initiator is 0.01 to 5% by weight based on the total amount of the composition. A more desirable ratio is from 0.01 to 1% by weight. Examples of photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184), 2,2-dimethoxy-1,2 -Diphenylethane-1-one (Irgacure 651), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, Irgacure 784, p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyla Lysine, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, and a mixture of 2,4-diethylxanthone and methyl p-dimethylaminobenzoate. Both Darocur and Irgacure are names of products sold by Ciba Specialty Chemicals Co., Ltd.

  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, and preferred examples thereof include 2,5-di (t-butyl) hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric acid hydrazide (DPPH), benzothiazine, 4-nitrosodimethyl. Aniline (NIDI), o-hydroxybenzophenone, p-methoxyphenol and the like.

  In order to improve the preservability of the polymerizable liquid crystal composition, an oxygen inhibitor may be added. The radical generated in the composition reacts with oxygen in the atmosphere to give a peroxide radical, and an undesirable reaction with the polymerizable compound is promoted. In order to prevent this, it is preferable to add an oxygen inhibitor. Examples of the oxygen inhibitor are phosphate esters and amines.

  In the following description, the liquid crystal film of the present invention obtained by polymerizing a polymerizable liquid crystal composition may be simply referred to as a liquid crystal film. The liquid crystal film can be formed as follows. First, a polymerizable liquid crystal composition is applied on a support substrate to form a coating film. Next, 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. Examples of support substrates that can be used are polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketone sulfide, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene. Plastic films such as terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetyl cellulose and partially saponified products thereof, epoxy resin, phenol resin, norbornene resin. On these films, when the polymerizable liquid crystal composition is used after being dissolved in a solvent, a protective layer which is not affected by the solvent may be formed. A supporting substrate that is attacked by the solvent can also be used in the present invention if a protective layer is formed. An example of a material used as the protective layer is polyvinyl alcohol. Furthermore, an anchor coat layer may be formed in order to improve the adhesion between the protective layer and the supporting substrate. As long as such an anchor coat layer enhances the adhesion between the protective layer and the support substrate, there is no problem even if it is an inorganic or organic material.

  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. 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

  The main object of the present invention is to form an optically anisotropic thin film layer in a liquid crystal cell. Therefore, the substrate used is particularly preferably a glass substrate that is not deformed and changes in optical properties when heated at 200 ° C. to 250 ° C.

  In order to facilitate coating or control the orientation of the liquid crystal phase, a surfactant may be added to the polymerizable liquid crystal composition of the present invention as long as the effects of the present invention are not impaired. Examples of surfactants are imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted Aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, lauryl amide propyl betaine, lauryl aminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkyl amines, perfluoroalkyl sulfonates, Perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkyl group Is a urethane having oligomer having a hydrophilic group, oligomers having a perfluoroalkyl group and a lipophilic group, and a perfluoroalkyl group. The addition amount of the surfactant varies depending on the kind of the surfactant, the composition ratio of the polymerizable liquid crystal composition, etc., but is preferably 20 ppm to 5% by weight, more preferably based on the polymerizable liquid crystal compound in the polymerizable liquid crystal composition. It is in the range of 100 ppm to 1% by weight.

  Prior to the formation of the coating film, the support substrate may be subjected to mechanical surface treatment such as rubbing. When forming a homeotropic alignment polymerizable liquid crystal layer, and when forming a homeotropic alignment liquid crystal film by polymerizing this polymerizable liquid crystal layer, it is usually unnecessary to perform a surface treatment such as rubbing. A rubbing treatment may be performed for the purpose of preventing alignment defects. When forming a homogeneous alignment, and when forming a liquid crystal film in which any of these polymerizable liquid crystal layers is polymerized to fix each alignment, a rubbing treatment is usually performed. The rubbing treatment may be performed directly on the support substrate, or an alignment film may be provided on the support substrate in advance, and the alignment film may be subjected to the rubbing treatment. Examples of the alignment film include polyimide, polyamide, and polyvinyl alcohol. A particularly preferred alignment film is polyimide. Any method can be used for rubbing, but usually a rubbing cloth made of materials such as rayon, cotton, polyamide, etc. is applied to a metal roll and moved while rotating the roll while in contact with the support substrate or alignment film. And a method of moving the supporting substrate side while the roll is fixed are employed. Depending on the type of the supporting substrate, silicon oxide can be deposited on the surface by gradient deposition to impart orientation ability.

  When producing a liquid crystal film, the polymerizable liquid crystal composition may be used as it is, or after dissolving it in a solvent and coating it, the solvent may be removed to produce a thin film. Preferred examples of the solvent include benzene, toluene, heptane, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, cyclopentanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, Dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylacetamide dimethyl Acetal, dimethylformamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, tetrahydrofuran (THF), chloroform, 1,4-dioxane, bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, tri Fluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, t-butyl alcohol, diacetone alcohol, ethanol, 2-propanol (isopropyl alcohol), glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene Glycol monomethyl ether, ethyl cellosolve, and butyl cellosolve. These can be used alone or as a mixed solvent.

  Examples of coating methods for obtaining a uniform film thickness include a micro gravure coating method, a gravure coating method, a wire bar coating method, a dip coating method, a spray coating method, and a meniscus 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.

  In order to disperse the organosilicon compound uniformly in the polymerizable liquid crystal composition, it may be diluted with a solvent. Such a solvent should just have the capability to dissolve an organosilicon compound and a compound (1) -compound (3), and should just select it according to the objective. Examples of preferred solvents include ethers such as THF, ketones such as acetone and methyl ethyl ketone, alcohols such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol and methoxymethyl alcohol, and acetates such as ethyl acetate and methyl acetate. , Chloroform, and acetonitrile.

  When a solvent is used, the solvent is removed after coating to form a coating film layer of a polymerizable liquid crystal composition having a uniform film thickness 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 in general and the fluidity | liquidity of a coating-film layer 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. However, in order to make the alignment of the liquid crystal molecules in the coating film more uniform, it is preferable to heat-treat the coating film that has undergone the drying step and then to perform photopolymerization.

  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 performed at or above the liquid crystal phase transition point of the polymerizable liquid crystal composition. An example of the heat treatment method is a method in which the coating film is heated to a temperature at which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase 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 80 ° C, and a more preferable range is room temperature to 70 ° 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.

The nematic alignment state of the polymerizable liquid crystal composition formed in the coating film is fixed by polymerizing the coating film 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 (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. It is. Preferred examples of the light source are a metal halide lamp, a xenon 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 coating layer of the polymerizable liquid crystal composition and passing only a specific wavelength region. The amount of light irradiated from the light source is ² to 5000 mJ / cm ² . 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.

A liquid crystal display device for forming a liquid crystal thin film having optical anisotropy obtained by polymerizing a polymerizable liquid crystal composition in a liquid crystal cell will be described below.
There are two planar substrates arranged in parallel, at least one of which is transparent. A transparent electrode and an alignment film are formed on at least one substrate, and a transparent electrode and an alignment film are formed on the other substrate as necessary. A liquid crystal medium is sandwiched between two opposing substrates. This liquid crystal medium exhibits at least two different alignment states depending on the voltage applied to the alignment film and the opposing electrode. These are the minimum necessary components for the liquid crystal cell. In the liquid crystal cell, an active element represented by a TFT and a color filter are formed so that the applied voltage can be adjusted for each pixel as necessary. A coat layer is provided. The liquid crystal cell is provided with a light source called a backlight and at least one polarizing plate as necessary. The polarizing plate exists at a position between the liquid crystal medium and the light source. A liquid crystal thin film obtained by aligning and polymerizing the polymerizable liquid crystal composition is formed on the flat substrate at a position sandwiched between the liquid crystal medium and the polarizing plate.
Although the configuration of the liquid crystal cell is shown in FIGS. 1 to 3 as the above specific example, the present invention is not limited to this.

  This liquid crystal thin film can be formed into a multilayer film directly or through a coating layer such as a substrate, an adhesive layer, or a polymer, with two or more different optical anisotropies such as alignment or retardation of the liquid crystal skeleton. It is also possible to independently form two or more regions.

  The merit of forming a liquid crystal thin film having optical anisotropy inside a liquid crystal cell by using a polymerizable liquid crystal composition capable of fixing a predetermined nematic alignment state by light irradiation is as follows. The liquid crystal thin film having specific optical anisotropy can be independently formed in the predetermined region. Although the specific example is shown below, this invention is not limited to this.

  First, as shown in FIG. 4A, a polymerizable liquid crystal composition is applied on a substrate according to the method described above to form a liquid crystal alignment A having desired optical anisotropy. Next, in this state, when light is irradiated using a photomask, the liquid crystal alignment is fixed by polymerization in the exposed region, and a liquid crystal thin film A having a certain optical anisotropy is formed accordingly. . On the other hand, in the region not exposed by the photomask, the liquid crystal alignment is not fixed without being polymerized (see FIG. 4B).

  The region where the liquid crystal alignment is not fixed without being exposed by the photomask can be removed by dissolving with a developer (see FIG. 4 (3)). It is also possible to form a liquid crystal thin film B having optical anisotropy different from that of the liquid crystal thin film A in that region (see FIG. 4 (4)).

  The polymerizable liquid crystal material mentioned in the present case has a thermotropic property in which the optical anisotropy changes depending on the temperature. By utilizing this property, the following method can be applied. That is, when a region which is shielded from light by the mask shown in FIG. 4 (2) and is not exposed and the liquid crystal alignment is not fixed is heated, optical anisotropy different from the previous liquid crystal alignment is developed (FIG. 4). (See (5)). For example, when the isotropic phase transition point or higher, the optical anisotropy becomes zero. That is, the liquid crystal thin film A ′ having optical anisotropy different from that of the previous liquid crystal thin film A is formed by performing exposure while heating at a constant temperature (see FIG. 4 (6)).

  When the liquid crystal thin film is independently formed in a predetermined region of the liquid crystal panel, a pattern accuracy of less than 10 μm is required. In order to obtain stable pattern accuracy, it is also effective to previously contain a polymerization inhibitor or an ultraviolet absorber described above. Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, or “Tinuvin PS” and “Tinuvin 213” manufactured by Ciba Specialty. , “Tinuvin 109”, “tinuvin 328”, “tinuvin 384-2”, “tinuvin 327”, and the like.

EXAMPLES The present invention will be described in detail by examples, but the present invention is not limited to these examples. The polymerization conditions and evaluation methods in the examples are shown below.
(1) 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.
(2) Confirmation of liquid crystal alignment state: Using an optical system in which a rotating / tilting stage is sandwiched between a rotatable polarizer and an analyzer, the obtained liquid crystal film is placed on the rotating / tilting stage, and the film surface is Retardation was measured and confirmed while tilting from the vertical direction.
(3) Glass substrate with alignment film that has been rubbed: A glass substrate having a thickness of 0.7 mm is spin-coated with an alignment agent solution containing polyimide as a main component, dried after the solvent is rubbed for 1 hour at 230 ° C. Processed.
(4) Film thickness: The thickness of the liquid crystal film in the glass substrate with a liquid crystal film was measured by using a stylus type surface shape measuring device by cutting out the liquid crystal film layer and measuring the step.
(5) Heat test: For a glass substrate with a liquid crystal film obtained by aligning a polymerizable liquid crystal composition on a glass substrate with an alignment film that has been rubbed and polymerizing and curing with UV, the initial values are retardation, film thickness, and spectral transmission. The rate was measured. Next, this glass substrate with a liquid crystal film is put into a hot air circulation type constant temperature dryer set at 200 ° C., taken out from the dryer after 1 hour, cooled to room temperature, and the retardation, film thickness and spectral transmittance are measured. It was measured. Again, this glass substrate with a liquid crystal film was put into a drier, and the retardation, film thickness, and spectral transmittance were similarly measured after 2 hours (3 hours in total) and further 5 hours (8 hours in total).
(6) Δn: The retardation and film thickness obtained for the liquid crystal film having homogeneous alignment were calculated as retardation / film thickness.
(7) The structure of the compound was confirmed by measuring by 500 MHz proton NMR.
(8) The melting point and transition temperature of the compound were observed with a polarizing microscope by placing the sample on a hot plate equipped with a melting point measuring device, raising the temperature at a rate of 1 ° C./min. C is a melting point, N is a nematic phase, and I is a transition temperature to an isotropic liquid.

（第１段階）
窒素雰囲気下、ジメチルスルホキシド（４００ｍｌ）にフルオレン（１００ｇ）とヨウ化メチル（２１２ｇ）を溶解した。ここに５０％水酸化ナトリウム水溶液（２００ｇ）とベンジルトリエチルアンモニウムクロライド（６．８０ｇ）を加えたところ激しく還流した。１時間撹拌後、反応溶液を水にあけ析出物をろ別した。残渣をヘプタンより再結晶し、９，９−ジメチルフルオレン（７３．５ｇ）を得た。
（融点：９１〜９３℃） [Synthesis Example 1]
<Synthesis of Compound (1-12)>

(First stage)
Under a nitrogen atmosphere, fluorene (100 g) and methyl iodide (212 g) were dissolved in dimethyl sulfoxide (400 ml). A 50% aqueous sodium hydroxide solution (200 g) and benzyltriethylammonium chloride (6.80 g) were added thereto, and the mixture was vigorously refluxed. After stirring for 1 hour, the reaction solution was poured into water and the precipitate was filtered off. The residue was recrystallized from heptane to obtain 9,9-dimethylfluorene (73.5 g).
(Melting point: 91-93 ° C.)

(Second stage)
Under a nitrogen atmosphere, 9,9-dimethylfluorene (68.4 g) was dissolved in dichloromethane (600 ml), and aluminum chloride (188 g) was added under ice cooling. Next, a solution of acetyl chloride (55.0 g) in dichloromethane (250 ml) was added dropwise, stirred for 30 minutes, the ice bath was removed, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into hydrochloric acid, and the dichloromethane layer was washed with a saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized with an acetone-ethanol mixed solvent to obtain 2,7-diacetyl-9,9-dimethylfluorene (81.9 g). (Melting point: 182-184 ° C)

(3rd stage)
Under a nitrogen atmosphere, 2,7-diacetyl-9,9-dimethylfluorene (23.0 g), acetic anhydride (33.2 g) and formic acid (74.0 g) were added to dichloromethane (300 ml), and sulfuric acid was added dropwise under ice cooling. . Next, 34.5% aqueous hydrogen peroxide (35.0 g) was added dropwise while maintaining the temperature at 10 ° C. or lower. The mixture was stirred at room temperature for 30 minutes and then heated to reflux for 5 hours. Water was added to the reaction solution for liquid separation, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, 10% sodium bisulfite, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (developing solvent: toluene) and recrystallized from ethanol to obtain 2,7-diacetoxy-9,9-dimethylfluorene (12.2 g).

(Fourth stage)
Under a nitrogen atmosphere, 2,7-diacetoxy-9,9-dimethylfluorene (5.00 g) and lithium hydroxide monohydrate (2.00 g) were dissolved in ethylene glycol (50 ml) and heated to reflux for 2 hours. The reaction solution was poured into hydrochloric acid, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was recrystallized from a chloroform-ethyl acetate mixed solvent to obtain 2,7-dihydroxy-9,9-dimethylfluorene (2.77 g). (Melting point: 177-180 ° C)

(5th stage)
Pyridine (934 g) was added to 6-chlorohexanol (800 g) under a nitrogen atmosphere and ice cooling. Acetic anhydride (1200 ml) was added thereto and heated under reflux for 3 hours, and then the reaction solution was poured into water and extracted with toluene. The organic layer was neutralized with a saturated aqueous sodium hydrogen carbonate solution, washed with water, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the concentrate was purified by distillation under reduced pressure to obtain 6-acetoxychlorohexane (983 g).

(6th stage)
Under a nitrogen atmosphere, 2-fluoro-4-hydroxybenzoic acid (268 g) was dissolved in N, N-dimethylformamide (3600 ml), sodium hydroxide (70.0 g) was added thereto, and the mixture was stirred at 40 ° C. for 30 minutes. . 6-Acetoxychlorohexane (312 g) was added, and the mixture was stirred at 80 ° C. for 5 hours. The reaction solution was poured into water and extracted with toluene. After separation, the toluene layer was washed with hydrochloric acid, aqueous sodium hydroxide solution and water, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, 268 g of concentrate was obtained. This concentrate was dissolved in ethanol (500 ml), and sodium hydroxide (98 g) was dissolved in water (800 ml) and added thereto. After heating under reflux for 2 hours, ethanol was distilled off and the concentrate was poured into hydrochloric acid. The precipitate was filtered off and recrystallized from ethanol to obtain compound 4- (6-hydroxyhexyloxy) -2-fluorobenzoic acid (189 g). (Melting point: 98-99 ° C)

  Under nitrogen atmosphere, tetrahydrofuran (500 ml) was charged with 4- (6-hydroxyhexyloxy) -2-fluorobenzoic acid (189 g), N, N-dimethylaniline (133 g), 2,6-di-tert-butyl-p- Cresol (0.80 g) was added. Acrylic acid chloride (100 g) was added dropwise and stirred at 60 ° C. for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was recrystallized from ethanol to obtain 4- (6-acryloyloxyhexyloxy) -2-fluorobenzoic acid (141 g).

Under a nitrogen atmosphere, dichloromethane (200 ml) and 4- (6-acryloyloxyhexyloxy) -2-fluorobenzoic acid (16.8 g), 2,7-dihydroxy-9,9-dimethylfluorene (5.56 g), 4 -Dimethylaminopyridine (0.15 g) was added, and a solution of N, N'-dicyclohexylcarbodiimide (11.1 g) in dichloromethane (20 ml) was added dropwise under ice cooling, followed by stirring at room temperature for 12 hours. The urea was filtered, water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by column chromatography (developing solvent: toluene / ethyl acetate = 19: 1) and recrystallized from a toluene-ethanol mixed solvent to obtain compound (1-12) (12.6 g).
Phase transition temperature: C 95 N 100 I (° C.). ¹ H-NMR (CDCl ₃ ; δ ppm): 8.08 (t, 2H), 7.72 (d, 2H), 7.29 (d, 2H), 7.19 (d, 2H), 6. 79 (dd, 2H), 6.70 (dd, 2H), 6.41 (dd, 2H), 6.13 (dd, 2H), 5.83 (dd, 2H), 4.19 (t, 4H) ), 4.04 (t, 4H), 1.82-1.88 (m, 4H), 1.71-1.76 (m, 4H), 1.51 (s, 6H), 1.44 1.57 (m, 8H).

（第１段階）
Liquid Crystals, Vol.30, No.8, August, 2003, 979−984に記載の方法により、４−（６−アクリロイルオキシヘキシルオキシ）安息香酸を合成した。窒素雰囲気下、ジクロロメタン（２００ｍｌ）に４−（６−アクリロイルオキシヘキシルオキシ）安息香酸（１２．０ｇ）、２，７−ジヒドロキシ−９，９−ジメチルフルオレン（４．２１ｇ）、４−ジメチルアミノピリジン（０．１１ｇ）を加え、氷冷下Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（８．２５ｇ）のジクロロメタン（２０ｍｌ）溶液を滴下して室温で１２時間撹拌した。ウレアをろ過し、ろ液に水を加え、塩酸、水酸化ナトリウム水溶液、水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下溶媒を留去した。残渣をカラムクロマトグラフィー（展開溶媒：トルエン／酢酸エチル＝１９：１）で分取後、トルエン−エタノール混合溶媒により再結晶し、化合物（１−５）（９．４１ｇ）を得た。
相転移温度：Ｃ １１３ Ｎ（℃）．
（等方相への転移点は重合したため確認できなかった。）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１７（ｄ，４Ｈ），７．７２（ｄ，２Ｈ），７．２８（ｄ，２Ｈ），７．１８（ｄｄ，２Ｈ），６．９８（ｄ，４Ｈ），６．４１（ｄｄ，２Ｈ），６．１３（ｄｄ，２Ｈ），５．８２（ｄｄ，２Ｈ），４．１９（ｔ，４Ｈ），４．０６（ｔ，４Ｈ），１．８３−１．８８（ｍ，４Ｈ），１．７１−１．７７（ｍ，４Ｈ），１．５１（ｓ，６Ｈ），１．４５−１．５８（ｍ，８Ｈ）。 [Synthesis Example 2]
<Synthesis of Compound (1-5)>

(First stage)
4- (6-acryloyloxyhexyloxy) benzoic acid was synthesized by the method described in Liquid Crystals, Vol. 30, No. 8, August, 2003, 979-984. 4- (6-acryloyloxyhexyloxy) benzoic acid (12.0 g), 2,7-dihydroxy-9,9-dimethylfluorene (4.21 g), 4-dimethylaminopyridine in dichloromethane (200 ml) under nitrogen atmosphere (0.11 g) was added, and a solution of N, N′-dicyclohexylcarbodiimide (8.25 g) in dichloromethane (20 ml) was added dropwise under ice cooling, followed by stirring at room temperature for 12 hours. The urea was filtered, water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by column chromatography (developing solvent: toluene / ethyl acetate = 19: 1) and recrystallized with a toluene-ethanol mixed solvent to obtain compound (1-5) (9.41 g).
Phase transition temperature: C 113 N (° C.).
(The transition point to the isotropic phase could not be confirmed because of polymerization.)
¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 4H), 7.72 (d, 2H), 7.28 (d, 2H), 7.18 (dd, 2H), 6. 98 (d, 4H), 6.41 (dd, 2H), 6.13 (dd, 2H), 5.82 (dd, 2H), 4.19 (t, 4H), 4.06 (t, 4H ), 1.83 to 1.88 (m, 4H), 1.71-1.77 (m, 4H), 1.51 (s, 6H), 1.45 to 1.58 (m, 8H).

（第１段階）
エタノール（１，５００ｍｌ）に３−（４−ヒドロキシフェニル）プロピオン酸（１１５０ｇ）を加えた溶液を撹拌しながら、硫酸（２３０ｇ）を１０分かけて滴下して、その後５時間還流させた。反応溶液を濃縮し、得られた濃縮液を水（１，０００ｍｌ）に注ぎ入れ、酢酸エチルを加えて攪拌した。分液した後、酢酸エチル層を飽和炭酸ナトリウム溶液で中和し、少量の水で水洗した後、無水硫酸マグネシウムで乾燥した。この酢酸エチル層から酢酸エチルおよび未反応成分を溶剤留去して、１４００ｇの濃縮物が得られた。濃縮物を減圧蒸留により精製して１，１４４ｇの３−（４−ヒドロキシフェニル）プロピオン酸エチルを得た。沸点は１６０℃／４．０ｈＰａであった。 [Synthesis Example 3]
<Synthesis of Compound (2-5)>

(First stage)
While stirring a solution obtained by adding 3- (4-hydroxyphenyl) propionic acid (1150 g) to ethanol (1,500 ml), sulfuric acid (230 g) was added dropwise over 10 minutes, and then refluxed for 5 hours. The reaction solution was concentrated, and the obtained concentrated solution was poured into water (1,000 ml), and ethyl acetate was added and stirred. After liquid separation, the ethyl acetate layer was neutralized with a saturated sodium carbonate solution, washed with a small amount of water, and dried over anhydrous magnesium sulfate. Ethyl acetate and unreacted components were distilled off from the ethyl acetate layer to obtain 1400 g of a concentrate. The concentrate was purified by vacuum distillation to give 1,144 g of ethyl 3- (4-hydroxyphenyl) propionate. The boiling point was 160 ° C./4.0 hPa.

(Second stage)
Ethyl 3- (4-hydroxyphenyl) propionate (400 g) was dissolved in dimethylformamide (2,800 ml). Sodium hydroxide (98 g) was added thereto, and the mixture was stirred at 40 ° C. for 30 minutes. The formation of salt could be observed visually. 6-Acetoxychlorohexane (515 g) was added and the mixture was stirred at 80 ° C. for 7 hours. The reaction solution was poured into water (2,000 ml), and toluene was added thereto and stirred. After separation, the toluene layer was washed with 6N hydrochloric acid, saturated sodium carbonate solution and water in this order, and dried over anhydrous magnesium sulfate. The solvent was distilled off from this toluene layer to obtain 709 g of a concentrate. Sodium hydroxide (185 g) was dissolved in water (400 ml), ethanol (600 ml) and concentrate 709 g were added thereto, heated and refluxed for 2 hours. The reaction solution was concentrated under reduced pressure using an evaporator, and the obtained concentrate was poured into 6N hydrochloric acid. The obtained slurry was filtered to obtain a solid, which was recrystallized with ethanol to obtain 281 g of (4- (6-hydroxyhexyloxy) phenyl) propionic acid. (Melting point: 109-112 ° C)

(Fourth stage)
(4- (6-Hydroxyhexyloxy) phenyl) propionic acid (200 g), N, N-dimethylaniline (100 g) and BHT (0.3 g) were dissolved in dioxane (1,000 ml). Acrylic acid chloride (74.3 g) was added dropwise thereto over 10 minutes and stirred at 60 ° C. for 5 hours. The reaction solution was poured into water, ethyl acetate was added and stirred. The ethyl acetate layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off from the ethyl acetate layer to obtain a solid. This solid was dissolved in toluene, poured into a large amount of heptane and reprecipitated to obtain 213 g of (4- (6-acryloyloxyhexyloxy) phenyl) propionic acid. (Melting point: 64-68 ° C)

(5th stage)
(4- (6-acryloxyhexyloxy) phenyl) propionic acid (150 g), 2,3-bis (trifluoromethyl) hydroquinone (52.2 g), BHT (0.75 g), dimethylaminopyridine (15 g) Dissolved in methylene chloride (900 ml). To this solution, a solution of DCC (N, N′-dicyclohexylcarbodiimide) (100 g) dissolved in methylene chloride (300 ml) was added dropwise over 1 hour. After further stirring for 2 hours, water was added to separate the layers. The methylene chloride layer was washed with 6N hydrochloric acid and 10% aqueous sodium hydroxide and dried over anhydrous magnesium sulfate. The concentrate obtained from this methylene chloride layer was purified by silica gel column chromatography to obtain 125 g of compound (2-5).
¹ H-NMR (CDCl ₃ ; δ ppm): 1.45 to 1.55 (m, 8H), 1.71-1.77 (m, 4H), 1.79-1.85 (m, 4H) , 2.92, (t, 4H, J = 7.5 Hz), 3.03 (t, 4H, 7.5 Hz), 3.97 (t, 4H, J = 6.5 Hz), 4.20 (t , 4H, J = 6.5 Hz), 5.84 (dd, 2H, J = 10 Hz and 1.3 Hz), 6.15 (dd, 2H, J = 17 Hz and 10 Hz), 6.42 (dd, 2H, J = 17 Hz and 1.3 Hz), 6.87 (d, 4H, J = 8.5 Hz), 7.18 (d, 4H, J = 8.5 Hz), 7.24 (s, 2H).

化合物（３−５）は、Macromolecules, 3938-3943, (23), (1990)に記載の方法により合成する。 [Synthesis Example 4]
<Synthesis of Compound (3-5)>

Compound (3-5) is synthesized by the method described in Macromolecules, 3938-3943, (23), (1990).

上記の組成物（ＭＩＸ１）にイルガキュアー９０７（重合開始剤；チバ・スペシャリティ・ケミカルズ製）を１重量％加え、さらにシクロペンタノンを３００重量％加えて、２５重量％シクロペンタノン溶液とした。この溶液を重合性液晶組成物溶液（ＭＩＸ１−１）とする。 <Preparation of Polymerizable Liquid Crystal Composition Solution (MIX1-1)>
(MIX1)

1% by weight of Irgacure 907 (polymerization initiator; manufactured by Ciba Specialty Chemicals) was added to the composition (MIX1), and then 300% by weight of cyclopentanone was added to obtain a 25% by weight cyclopentanone solution. This solution is referred to as “polymerizable liquid crystal composition solution (MIX1-1)”.

<Preparation of optically anisotropic thin film>
A polymerizable liquid crystal composition solution (MIX1-1) is applied to a glass substrate with an alignment film that has been rubbed by spin coating, heated at 70 ° C. for 3 minutes to remove the solvent, align the liquid crystal molecules, and then UV light. A glass substrate with a liquid crystal film having homogeneous orientation was obtained by polymerization under a nitrogen stream. The result of measuring the retardation while tilting the glass substrate with a liquid crystal film from the direction perpendicular to the film surface in the rubbing direction is shown in FIG.

化合物（１−１２）を化合物（Ａ）に替えた以外は実施例１と同様にして重合性液晶組成物溶液を調整した。得られた重合性液晶組成物溶液を用い、実施例１と同様にしてホモジニアス配向を有する光学フィルムを得た。この液晶フィルム付きガラス基板のレタデーションの傾斜角依存性は実施例１と同様の傾向であった。化合物（Ａ）は特開２００３−２３８４９１公報に記載の方法で合成した。 [Comparative Example 1]

A polymerizable liquid crystal composition solution was prepared in the same manner as in Example 1 except that the compound (1-12) was changed to the compound (A). Using the obtained polymerizable liquid crystal composition solution, an optical film having homogeneous alignment was obtained in the same manner as in Example 1. The dependence of the retardation of the glass substrate with a liquid crystal film on the inclination angle had the same tendency as in Example 1. Compound (A) was synthesized by the method described in JP-A-2003-238491.

(Evaluation 1) About the glass substrate with a liquid crystal film obtained in Example 1 and Comparative Example 1, Δn of the liquid crystal film (before the heating test), retardation before and after the heating test, relative change rate with respect to the initial value of the film thickness, yellowing The state is shown in Table 1. The spectral transmittance characteristics of the glass substrate with a liquid crystal film before and after the heating test are shown in FIG.

<Preparation of polymerizable liquid crystal composition solution (MIX2-1)>
A composition composed of 80% by weight of the compound (1-12) and 20% by weight of the compound (2-5) was designated as (MIX2), and to this was added Irgacure 907 having a weight ratio of 0.01, and further a weight ratio of 3.0. Cyclopentanone was added to obtain a cyclopentanone solution having a solute concentration of 25% by weight. The solution thus obtained is designated as a polymerizable liquid crystal composition solution (MIX2-1).

  A polymerizable liquid crystal composition solution (MIX2-1) is applied to a glass substrate with a facing film that has been rubbed by spin coating, heated at 70 ° C. for 3 minutes to remove the solvent, align liquid crystal molecules, and then UV To obtain a glass substrate with a liquid crystal film having homogeneous orientation. The dependence of the retardation of the glass substrate with a liquid crystal film on the inclination angle had the same tendency as in Example 1.

[Comparative Example 2]
A polymerizable liquid crystal composition solution was prepared in the same manner as in Example 2 except that the compound (1-12) was changed to the compound (A). Using the obtained polymerizable liquid crystal composition solution, an optical film having homogeneous alignment was obtained in the same manner as in Example 4. The dependence of the retardation of the glass substrate with a liquid crystal film on the inclination angle had the same tendency as in Example 1.

(Evaluation 2) About the glass substrate with a liquid crystal film obtained in Example 2 and Comparative Example 2, Δn of the liquid crystal film (before the heating test), retardation before and after the heating test, relative change rate with respect to the initial value of the film thickness, yellowing The state is shown in Table 1.

<Preparation of polymerizable liquid crystal composition solution (MIX3-1)>
The composition consisting of 70% by weight of the compound (1-12) and 30% by weight of the compound (3-5) was defined as (MIX3), and Irgacure 907 having a weight ratio of 0.01 was added to the (MIX3), and the weight ratio was further increased. 3.445 cyclopentanone was added to obtain a cyclopentanone solution having a solute concentration of 22.5% by weight. The solution thus obtained is designated as a polymerizable liquid crystal composition solution (MIX3-1).

  The polymerizable liquid crystal composition solution (MIX3-1) was applied to a glass substrate with an alignment film that had been rubbed by a bar coater, heated at 70 ° C. for 3 minutes to remove the solvent, and liquid crystal molecules were aligned. Then, the glass substrate with a liquid crystal film which has a hybrid orientation was obtained by superposing | polymerizing under a nitrogen stream with an ultraviolet-ray. The result of measuring the retardation while tilting the glass substrate with a liquid crystal film from the direction perpendicular to the film surface to the rubbing direction is shown in FIG.

[Comparative Example 3]
A polymerizable liquid crystal composition solution was prepared in the same manner as in Example 3 except that the compound (1-12) was changed to the compound (A). Using the obtained polymerizable liquid crystal composition solution, an optical film having hybrid alignment was obtained in the same manner as in Example 3. The inclination angle dependency of the retardation of the glass substrate with a liquid crystal film had the same tendency as in Example 3.

(Evaluation 3) Table 1 shows the retardation before and after the heating test, the relative change rate with respect to the initial value of the film thickness, and the yellowing state of the glass substrate with a liquid crystal film obtained in Example 3 and Comparative Example 3.

<Preparation of polymerizable liquid crystal composition solution (MIX4-1)>
The following amino group-containing silicon compound was added to the composition (MIX1) prepared in Example 1 at a weight ratio of 0.05, Irgacure 907 having a weight ratio of 0.01 was added, and toluene having a weight ratio of 3.0 was further added. Was added to obtain a toluene solution having a solute concentration of 25% by weight. The solution thus obtained is designated as a polymerizable liquid crystal composition solution (MIX4-1).

  A polymerizable liquid crystal composition solution (MIX4-1) is applied to a glass substrate by spin coating, and the liquid crystal molecules are aligned by removing the solvent by heating at 70 ° C. for 3 minutes, and then polymerized under a nitrogen stream by ultraviolet rays. Thus, a glass substrate with a liquid crystal film having homeotropic alignment was obtained. The result of measuring the retardation while tilting the glass substrate with a liquid crystal film from the direction perpendicular to the film surface to the rubbing direction is shown in FIG.

[Comparative Example 4]
The polymerizable liquid crystal composition was the same as in Example 4 except that the compound (1-12) was replaced with the compound (A), and the addition amount of the silicon compound was changed to a weight ratio of 0.1 with respect to the polymerizable liquid crystal composition. A solution was prepared. Using this polymerizable liquid crystal composition solution, an optical film having homeotropic alignment was obtained in the same manner as in Example 4. The inclination angle dependency of retardation of the glass substrate with a liquid crystal film had the same tendency as in Example 4.

(Evaluation 4) Table 1 shows the retardation (50 °) before and after the heating test, the relative rate of change with respect to the initial value of the film thickness, and the state of yellowing of the glass substrate with a liquid crystal film obtained in Example 4 and Comparative Example 4. Indicated. The retardation (50 °) is a retardation measured by placing the obtained liquid crystal film on a rotation / tilting stage and tilting it by 50 ° from the vertical direction with respect to the film surface.

(Table 1) Evaluation results for the obtained liquid crystal film

From this table, the homogeneously aligned liquid crystal thin film (Examples 1 and 2), the hybrid aligned liquid crystal thin film (Example 3), and the homeotropic aligned liquid crystal thin film (Example 4) prepared from the composition of the present invention are as follows. It can be seen that, compared with a liquid crystal thin film prepared from a composition containing a compound having a monomethylfluorene skeleton as a main component, the decrease in the film thickness after heating at 200 ° C. is small, and the coloration to yellow is also small.
(Evaluation 5) Next, verification regarding the formation of a liquid crystal thin film having specific optical anisotropy in a predetermined region of the substrate was performed.
<Preparation of polymerizable liquid crystal composition solution (MIX5-1)>
A composition comprising 75% by weight of the compound (1-12) and 25% by weight of the compound (2-5) is defined as (MIX4), and 0.01% by weight of Irgacure 651 and 0.001 by weight of BHT are added thereto. Further, cyclopentanone having a weight ratio of 3.0 was added to obtain a cyclopentanone solution having a solute concentration of 25% by weight. The solution thus obtained is designated as a polymerizable liquid crystal composition solution (MIX5-1). This polymerizable liquid crystal composition solution (MIX5-1) is applied to a glass substrate with an alignment film that has been rubbed by spin coating, heated at 70 ° C. for 3 minutes to remove the solvent, and the liquid crystal molecules are aligned. In the hot plate, it was confirmed that the isotropic phase point transfer was 69 ° C. at a temperature rise of 1 ° C./min.

  A polymerizable liquid crystal composition solution (MIX5-1) is applied to a glass substrate with an alignment film that has been rubbed by spin coating, heated at 70 ° C. for 3 minutes to remove the solvent, and then allowed to stand at room temperature for 2 minutes to leave liquid crystal molecules. After orientation, the polymer was polymerized under a nitrogen stream by ultraviolet rays through a mask. Next, this was left for 3 minutes in a hot pouch heated to 80 ° C., and polymerized under a nitrogen stream by ultraviolet rays without passing through a mask while maintaining the state heated by the hot plate. FIG. 9 shows the result of observing this substrate with a polarizing microscope. The bright part in FIG. 9 is a region that was not shielded by the mask when irradiated with ultraviolet rays at room temperature, and its retardation was 185 nm. That is, this region was confirmed to be optically anisotropic. The dark part in FIG. 9 is an area shielded from light by the mask, and the retardation of this area is less than 1 nm. That is, it was confirmed that this region was not optically anisotropic. A commercially available resolution test target (negative pattern) was used as the mask, and the mask was placed on a substrate with a spacer formed by hollowing out a film of about 50 μm so as not to directly touch the coated surface of the polymerizable liquid crystal.

  In the same manner as in Example 5, the liquid crystal molecules were aligned for 2 minutes at room temperature, and then polymerized under a nitrogen stream with ultraviolet rays through a mask was immersed in acetone for 30 seconds. Observation with a polarizing microscope confirmed that bright and dark regions were formed as in FIG. 9 of Example 5. The bright area is the area that was not shielded by the mask when irradiated with ultraviolet rays at room temperature. In this area, the liquid crystal thin film formed with the liquid crystal alignment fixed was eroded even when immersed in acetone. It is maintained without. The dark region is a region where the liquid crystal alignment is not fixed. That is, this region is a region where the polymerization has not progressed because it is shielded from light, and it is determined that the polymerizable liquid crystal material has been completely removed by acetone.

  According to the present invention, a liquid crystal thin film having heat resistance that can be formed inside a liquid crystal cell can be obtained. The alignment modes of the optically anisotropic liquid crystal thin film are homogeneous alignment, hybrid alignment, and homeotropic alignment, and are applied to the viewing angle compensation of liquid crystal display devices such as TN mode, IPS mode, VA mode, OCB mode, and ASV mode. Can do.

Specific example 1 of liquid crystal cell (liquid crystal cell in which one layer of optically anisotropic liquid crystal thin film is formed inside the liquid crystal cell). Specific example 2 of a liquid crystal cell (a liquid crystal cell formed by laminating two optically anisotropic liquid crystal thin films having different alignment states inside a liquid crystal cell). Specific example 3 of a liquid crystal cell (a liquid crystal cell formed by coating an optically anisotropic liquid crystal thin film obtained by polymerizing a plurality of polymerizable liquid crystal compositions with adjusted retardation separately for each pixel inside the liquid crystal cell). 1 is an outline of a process showing an example of a method for forming a liquid crystal thin film having specific optical anisotropy in a predetermined region of a substrate. The result of measuring the retardation of the glass substrate with a liquid crystal thin film obtained in Example 1 while inclining from the direction perpendicular to the film surface. Spectral transmittance measured before and after conducting a heat resistance test at 200 ° C. for 8 hours on the glass substrate with a liquid crystal film obtained in Example 1 and Comparative Example 1. The result of having measured the retardation, making it incline from a perpendicular direction with respect to a film surface about the glass substrate with a liquid crystal thin film obtained in Example 3. FIG. The result of measuring the retardation of the glass substrate with a liquid crystal thin film obtained in Example 4 while inclining from the vertical direction to the rubbing direction with respect to the film surface. The polarization microscope observation result of the glass substrate with a liquid crystal thin film obtained in Example 5. FIG.

Explanation of symbols

31-a: (Glass) substrate 31-b: (Glass) substrate 31-a: (Glass) substrate 31-b: (Glass) substrate 32: TFT element 33: Overcoat layer 34: Color filter 35: Overcoat layer 36-a: Alignment film 36-b: Alignment film 36-c: Alignment film 37: Aligned and polymerized polymerizable liquid crystal composition 37-a: Aligned and polymerized polymerizable liquid crystal composition Liquid crystal thin film 37-b: Liquid crystal thin film 38-a: Transparent electrode 38-b: Transparent electrode 39: Liquid crystal medium 40: Overcoat layer obtained by aligning and polymerizing a polymerizable liquid crystal composition

Claims (23)

A composition comprising a compound represented by formula (1) and at least one of a compound represented by formula (2) and a compound represented by formula (3), wherein the composition is represented by formula (1) The ratio of the compound represented by formula (1) is 50 to 99% by weight based on the total amount of the compound represented by formula (2) and the compound represented by formula (3), and the formula ( 2) A polymerizable liquid crystal composition in which the proportion of the compound represented by 2) is 0 to 50% by weight and the proportion of the compound represented by formula (3) is 0 to 50% by weight:

Where R is alkyl having 1 to 4 carbon atoms; W ¹ and W ² are independently hydrogen, chlorine, fluorine or —CH ₃ ; W ³ and W ⁴ are independently hydrogen, chlorine, fluorine , —CH ₃ or —CF ₃ ; W ⁵ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, chlorine, fluorine, —CN or —OCF ₃ ; X is a single bond, —CH 3 ═CH— or —CH ₂ CH ₂ —; Z is a single bond, —COO—, —OCO— or —CH ₂ CH ₂ —; and q is an integer of 1-20. A composition comprising a compound represented by formula (4) and at least one of a compound represented by formula (5) and a compound represented by formula (6), wherein the composition is represented by formula (4): The proportion of the compound represented by formula (4) is 50 to 90% by weight based on the total amount of the compound represented by formula (5) and the compound represented by formula (6). The proportion of the compound represented by 5) is 0 to 50% by weight, the proportion of the compound represented by formula (6) is 0 to 50% by weight, and the proportion of the compound represented by formula (5) And a polymerizable liquid crystal composition in which the total ratio of the compounds represented by formula (6) is 10 to 50% by weight:

Where W ² is hydrogen or fluorine; and q is an integer from 2 to 10.   The proportion of the compound represented by the formula (4) is 50 to 80% by weight, the proportion of the compound represented by the formula (5) is 10 to 40% by weight, and the compound represented by the formula (6) The ratio is 10 to 40% by weight, and the sum of the ratio of the compound represented by the formula (5) and the ratio of the compound represented by the formula (6) is 20 to 50% by weight. Polymerizable liquid crystal composition. The proportion of the compound represented by the formula (4) is 50 to 80% by weight, the proportion of the compound represented by the formula (5) is 10 to 40% by weight, and the compound represented by the formula (6) The ratio is 10 to 40% by weight, the sum of the ratio of the compound represented by formula (5) and the ratio of the compound represented by formula (6) is 20 to 50% by weight, and W ² is hydrogen. The polymerizable liquid crystal composition according to claim 2, wherein   The proportion of the compound represented by the formula (4) is 50 to 90% by weight, the proportion of the compound represented by the formula (5) is 10 to 50% by weight, and the compound represented by the formula (6) The polymerizable liquid crystal composition according to claim 2, wherein the ratio of is 0% by weight.   The proportion of the compound represented by formula (4) is 50 to 90% by weight, the proportion of the compound represented by formula (5) is 0% by weight, and the proportion of the compound represented by formula (6) The polymerizable liquid crystal composition according to claim 2, wherein is 10 to 50% by weight. A composition further containing a compound represented by formula (7), wherein the proportion of the compound represented by formula (7) is 1 to 20% by weight based on the total amount of the composition. The polymerizable liquid crystal composition according to any one of the above.

Where R ² is hydrogen or alkyl having 1 to 8 carbon atoms; R ³ is alkyl having 1 to 8 carbon atoms; Y is alkylene having 1 to 20 carbon atoms; and n is 0 to 2 It is an integer. In formula (7), Y is trimethylene, R ³ is ethyl, n is 0; and the proportion of the compound of formula (7) is 1 to 10% by weight. The polymerizable liquid crystal composition according to the description.   The polymeric liquid crystal layer formed by apply | coating the polymeric liquid crystal composition of any one of Claims 1-8 on a glass substrate.   The polymerizable liquid crystal layer according to claim 9, wherein the glass substrate is a surface-treated glass substrate.   The polymerizable liquid crystal layer according to claim 10, wherein the surface-treated glass substrate is a glass substrate obtained by providing a polyimide alignment film on the surface and rubbing it.   The polymerizable liquid crystal composition according to any one of claims 3 to 5 is formed by applying a polyimide alignment film on a surface of a glass substrate that has been subjected to a rubbing treatment, and the alignment state is homogeneous alignment. Polymerizable liquid crystal layer.   A polymerizable liquid crystal layer formed by coating the polymerizable liquid crystal composition according to claim 6 on a glass substrate on which a polyimide alignment film is provided and rubbed, and the alignment state is hybrid alignment.   A polymerizable liquid crystal layer formed by applying the polymerizable liquid crystal composition according to claim 7 or 8 on a glass substrate and having an alignment state of homeotropic alignment.   An optically anisotropic liquid crystal thin film obtained by polymerizing the polymerizable liquid crystal layer according to claim 12 and having a fixed orientation.   The optically anisotropic liquid crystal thin film according to claim 15, which has a thickness of 0.05 to 5 μm.   An optical element having the optically anisotropic liquid crystal thin film according to claim 15.   A retardation plate having the optically anisotropic liquid crystal thin film according to claim 15.   A polarizing plate comprising the optically anisotropic liquid crystal thin film according to claim 15.   An optical element having the retardation plate according to claim 18 or the polarizing plate according to claim 19.   A display device comprising the retardation plate according to claim 18 or the polarizing plate according to claim 19.   A liquid crystal display device comprising the retardation plate according to claim 18 or the polarizing plate according to claim 19. A liquid crystal display device in which the optically anisotropic liquid crystal thin film according to claim 15 is formed on an inner surface of a liquid crystal cell.

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