KR101102680B1 - Polymerizable Compound - Google Patents

Abstract

The present invention provides a polymerizable compound capable of producing a liquid crystal display device having high contrast, high voltage retention, and low residual DC voltage by polymerization in a liquid crystal display device.

In addition, the present invention provides a polymerizable compound represented by the following formula (1).

<Formula 1>

RY ¹ -AY ² -Z

In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, and A is a divalent selected from a cyclohexylene group, a bicyclohexylene group, a phenylene group, a biphenylene group, a terphenylene group and a naphthylene group. It is an organic group, Y <^1> and Y <^2> are mutually independently the bonding group chosen from a single bond, an ether bond, an ester bond, and an amide bond, and Z is a polymeric functional group containing an ethylenically unsaturated bond.

Polymerizable compound, liquid crystal aligning film, liquid crystal display element, contrast, voltage retention, residual DC voltage, polyamic acid

Description

Polymerizable Compound

1 is an NMR spectrum diagram of a polymerizable compound (Example 1) of the present invention.

2 is an NMR spectral diagram of the polymerizable compound (Example 2) of the present invention.

The present invention relates to a polymerizable compound. In more detail, it is related with the polymeric compound useful for a liquid crystal display element.

Currently, as a liquid crystal display element, a liquid crystal aligning film containing polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a substrate for a liquid crystal display element, and two of them are disposed to face each other in the gap thereof. A so-called twisted nematic liquid crystal cell in which a nematic liquid crystal layer having dielectric anisotropy is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. TN type liquid crystal display elements having a well-known type are well known. Moreover, in recent years, STN (Super Twisted Nematic) type liquid crystal display element which has high contrast compared with TN type liquid crystal display element and its visual dependence is developed. This STN type liquid crystal display element uses a mixture of a nematic liquid crystal and a chiral agent, which is an optically active substance, as a liquid crystal, and is produced when the long axis of the liquid crystal molecule is continuously twisted over 180 degrees between substrates. It is to use the birefringence effect. Orientation of the liquid crystal in these TN type liquid crystal display elements and STN type liquid crystal display elements is expressed by the liquid crystal aligning film to which the rubbing process was performed normally.

For these, "liquid crystal" vol. 3 No. 2 117 (1999) and Japanese Patent Laid-Open No. 11-258605, MVA system for forming projections on ITO to control the alignment direction of liquid crystal, or "liquid crystal" vol. 3 No. 4, 272 (1999), an EVA method that studies the electrode structure and controls the orientation direction, "Jpn Appl. Phys." A vertical alignment liquid crystal display element such as a photo alignment system in which an alignment film is modified by light irradiation as described in Vol 36 428 (1997) to control the alignment direction has been proposed. Such a vertically-aligned liquid crystal display element is excellent also in a manufacturing process aspect, such as being excellent in viewing angle, contrast, etc., and not having to perform a rubbing process in formation of a liquid crystal aligning film. However, compared with the TN type and STN type liquid crystal display elements mentioned above, performance is still inadequate, and the performance improvement regarding the vertical alignment property and the afterimage erase time of a liquid crystal display element is desired especially.

On the other hand, in the orientation control of the liquid crystal, in particular, the homeotropic alignment orientated perpendicularly to the substrate surface only involves mixing a compound having a hydrophobic group such as lecithin or hexadecyltrimethylammonium bromide in the liquid crystal or immersing the substrate in such a solution. Also, it is known that orientation control can be easily achieved without taking means such as a rubbing treatment.

Such vertically oriented liquid crystal display elements are particularly desired to provide a strong orientation control force in the polar angle direction that defines the initial orientation.

 In the case of driving at a constant frame period, it is preferable that the voltage holding ratio (voltage holding ratio in the frame main period) of the liquid crystal display element is high in order to obtain a good contrast display.

In addition, it is preferable that the DC voltage remaining after releasing the applied voltage (hereinafter referred to as "remaining DC voltage") is preferably as low as possible from the viewpoint of preventing the decrease in contrast due to the afterimage and the phenomenon of sticking of the image.

However, only the conventional vertical liquid crystal aligning film has actually provided no liquid crystal display element that satisfies high contrast, high voltage retention and low residual DC voltage in its liquid crystal display element.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching based on the above circumstances, the present inventors can manufacture a liquid crystal display element which has high contrast, high voltage retention, and low residual DC voltage by polymerizing a specific polymeric compound in a liquid crystal display element. I found something.

An object of the present invention is to provide a polymerizable compound useful for solving the above problems.

Another object of the present invention is to provide a polymerizable compound useful for a liquid crystal alignment film in a liquid crystal display device.                         

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by a polymerizable compound represented by the following general formula (1).

RY ¹ -AY ² -Z

In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, and A is a divalent selected from a cyclohexylene group, a bicyclohexylene group, a phenylene group, a biphenylene group, a terphenylene group and a naphthylene group. It is an organic group, Y <^1> and Y <^2> are mutually independently the bonding group chosen from a single bond, an ether bond, an ester bond, and an amide bond, and Z is a polymeric functional group containing an ethylenically unsaturated bond. Provided that the alkyl group of R may be substituted with an alkoxyl group having 1 to 10 carbon atoms, a halogen atom or a phenyl group, and the divalent organic group of A may be an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogen atom or It may be substituted by the phenyl group.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The polymerizable compound of the present invention is represented by the formula (1). Here, in Formula 1, R is a linear or branched alkyl group having 1 to 30 carbon atoms, preferably a linear or branched alkyl group having 6 to 20 carbon atoms. These alkyl groups may be substituted with a C1-C10 alkoxyl group, a halogen atom, or a phenyl group.

A is a divalent organic group selected from a cyclohexylene group, a bicyclohexylene group, a phenylene group, a biphenylene group, a terphenylene group and a naphthylene group, preferably a cyclohexylene group and a bicyclohexylene Group, a phenylene group, or a biphenylene group. These divalent organic groups may be substituted with a C1-C10 alkyl group, a C1-C10 monoxyl group, a halogen atom, or a phenyl group.

In addition, Y ¹ and Y ² are each independently a bond group selected from a single bond, an ether bond, an ester bond and an amide bond, preferably Y ¹ is a single bond or an ether bond, and Y ² is an ester bond. Z is a polymerizable functional group which combines an ethylenically unsaturated bond, Preferably it is an ethenyl group and 1-methylethenyl group. As the group represented by ZY ^2-, acryloyl group and methacryloyl group are particularly preferable.

Specific examples of the compound represented by Formula 1 include 2-hexylphenyl acrylate, 2-heptylphenyl acrylate, 2-octylphenyl acrylate, 2-decylphenyl acrylate, 2-dodecylphenyl acrylate, 2- Hexadecylphenyl acrylate, 2-octadecylphenyl acrylate, 2-hexylphenyl methacrylate, 2-heptylphenyl methacrylate, 2-octylphenyl methacrylate, 2-decylphenyl methacrylate, 2-dodecyl Phenyl methacrylate, 2-hexadecylphenyl methacrylate, 2-octadecylphenyl methacrylate, 2-hexyloxyphenyl acrylate, 2-heptyloxyphenyl acrylate, 2-octyloxyphenyl acrylate, 2-nonyl Oxyphenyl acrylate, 2-decyloxyphenyl acrylate, 2-dodecyloxyphenyl acrylate, 2-hexadecyloxyphenyl acrylate, 2-octadecyloxyphenyl acrylate, 2-hexyloxyphenyl methacrylate , 2-heptyloxyphenyl methacrylate, 2-octyloxyphenyl methacrylate, 2-nonyloxyphenyl methacrylate, 2-decyloxyphenyl methacrylate, 2-dodecyloxyphenyl methacrylate, 2-hexa Decyloxyphenyl methacrylate, 2-octadecyloxyphenyl methacrylate, 2-hexylcyclohexyl acrylate, 2-heptylcyclohexyl acrylate, 2-octylcyclohexyl acrylate, 2-nonylcyclohexyl acrylate, 2-decylcyclohexyl acrylate, 2-dodecylcyclohexyl acrylate, 2-hexadecylcyclohexyl acrylate, 2-octadecylcyclohexyl acrylate, 2-hexylcyclohexyl methacrylate, 2- Heptylcyclohexyl methacrylate, 2-octylcyclohexyl methacrylate, 2-nonylcyclohexyl methacrylate, 2-decylcyclohexyl methacrylate, 2-dodecylcyclohexyl methacrylate, 2-hexadecyl Cle Hexyl methacrylate, 2-octadecylcyclohexyl methacrylate, 2-hexyloxycyclohexyl acrylate, 2-heptyloxycyclohexyl acrylate, 2-octyloxycyclohexyl acrylate, 2-nonyloxycyclohexyl acrylic Late, 2-decyloxycyclohexyl acrylate, 2-dodecyloxycyclohexyl acrylate, 2-hexadecyloxycyclohexyl acrylate, 2-octadecyloxycyclohexyl acrylate, 2-hexyloxycyclohexyl methacrylate , 2-heptyloxycyclohexyl methacrylate, 2-octyloxycyclohexyl methacrylate, 2-nonyloxycyclohexyl methacrylate, 2-decyloxycyclohexyl methacrylate, 2-dodecyloxycyclohexyl methacrylate Latex, 2-hexadecyloxycyclohexyl methacrylate, 2-octadecyloxycyclohexyl methacrylate, 3-hexylphenyl acrylate, 3-heptylphenyl acrylic , 3-octylphenyl acrylate, 3-decylphenyl acrylate, 3-dodecylphenyl acrylate, 3-hexadecylphenyl acrylate, 3-octadecylphenyl acrylate, 3-hexylphenyl methacrylate, 3- Heptylphenyl methacrylate, 3-octylphenyl methacrylate, 3-decylphenyl methacrylate, 3-dodecylphenyl methacrylate, 3-hexadecylphenyl methacrylate, 3-octadecylphenyl methacrylate, 3 -Hexyloxyphenyl acrylate, 3-heptyloxyphenyl acrylate, 3-octyloxyphenyl acrylate, 3-nonyloxyphenyl acrylate, 3-decyloxyphenyl acrylate, 3-dodecyloxyphenyl acrylate, 3- Hexadecyloxyphenyl acrylate, 3-octadecyloxyphenyl acrylate, 3-hexyloxyphenyl methacrylate, 3-heptyloxyphenyl methacrylate, 3-octyloxyphenyl methacrylate, 3-nonyloxyphenyl methacrylate Rate, 3-decyloxyphenyl methacrylate, 3-dodecyloxyphenyl methacrylate, 3-hexadecyloxyphenyl methacrylate, 3-octadecyloxyphenyl methacrylate, 3-hexylcyclohexyl acrylate, 3- Heptylcyclohexyl acrylate, 3-octylcyclohexyl acrylate, 3-nonylcyclohexyl acrylate, 3-decylcyclohexyl acrylate, 3-dodecylcyclohexyl acrylate, 3-hexadecylcyclohexyl acrylate, 3-octadecylcyclohexyl acrylate, 3-hexylcyclohexyl methacrylate, 3-heptylcyclohexyl methacrylate, 3-octylcyclohexyl methacrylate, 3-nonylcyclohexyl methacrylate, 3-de Silcyclohexyl methacrylate, 3-dodecylcyclohexyl methacrylate, 3-hexadecylcyclohexyl methacrylate, 3-octadecylcyclohexyl methacrylate, 3-hexyloxycyclohexyl acrylate, 3 -Heptyloxycyclohexyl acrylate, 3-octyloxycyclohexyl acrylate, 3-nonyloxycyclohexyl acrylate, 3-decyloxycyclohexyl acrylate, 3-dodecyloxycyclohexyl acrylate, 3-hexadecyl Oxycyclohexyl acrylate, 3-octadecyloxycyclohexyl acrylate, 3-hexyloxycyclohexyl methacrylate, 3-heptyloxycyclohexyl methacrylate, 3-octyloxycyclohexyl methacrylate, 3-nonyloxy Cyclohexyl methacrylate, 3-decyloxycyclohexyl methacrylate, 3-dodecyloxycyclohexyl methacrylate, 3-hexadecyloxycyclohexyl methacrylate, 3-octadecyloxycyclohexyl methacrylate, 4 -Hexylphenyl acrylate, 4-heptylphenyl acrylate, 4-octylphenyl acrylate, 4-decylphenyl acrylate, 4-dodecylphenyl acrylate, 4-hexadecylpe Acrylate, 4-octadecylphenyl acrylate, 4-hexylphenyl methacrylate, 4-heptylphenyl methacrylate, 4-octylphenyl methacrylate, 4-decylphenyl methacrylate, 4-dodecylphenyl methacrylate Latex, 4-hexadecylphenyl methacrylate, 4-octadecylphenyl methacrylate, 4-hexyloxyphenyl acrylate, 4-heptyloxyphenyl acrylate, 4-octyloxyphenyl acrylate, 4-nonyloxyphenyl acrylic 4-decyloxyphenyl acrylate, 4-dodecyloxyphenyl acrylate, 4-hexadecyloxyphenyl acrylate, 4-octadecyloxyphenyl acrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxy Phenyl methacrylate, 4-octyloxyphenyl methacrylate, 4-nonyloxyphenyl methacrylate, 4-decyloxyphenyl methacrylate, 4-dodecyloxyphenyl methacrylate, 4-hexadecyloxyphenyl methacrylate relay , 4-octadecyloxyphenyl methacrylate, 4-hexylcyclohexyl acrylate, 4-heptylcyclohexyl acrylate, 4-octylcyclohexyl acrylate, 4-nonylcyclohexyl acrylate, 4-decylcyclo Hexyl acrylate, 4-dodecylcyclohexyl acrylate, 4-hexadecylcyclohexyl acrylate, 4-octadecylcyclohexyl acrylate, 4-hexylcyclohexyl methacrylate, 4-heptylcyclohexyl methacryl 4-octylcyclohexyl methacrylate, 4-nonylcyclohexyl methacrylate, 4-decylcyclohexyl methacrylate, 4-dodecylcyclohexyl methacrylate, 4-hexadecylcyclohexyl methacrylate , 4-octadecylcyclohexyl methacrylate, 4-hexyloxycyclohexyl acrylate, 4-heptyloxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, 4-nonyloxycyclohexyl arc Relate, 4-decyloxycyclohexyl acrylate, 4-dodecyloxycyclohexyl acrylate, 4-hexadecyloxycyclohexyl acrylate, 4-octadecyloxycyclohexyl acrylate, 4-hexyloxycyclohexyl methacryl 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decyloxycyclohexyl methacrylate, 4-dodecyloxycyclohexyl meta Acrylate, 4-hexadecyloxycyclohexyl methacrylate, and 4-octadecyloxycyclohexyl methacrylate are mentioned. Among them, 4-hexylphenyl acrylate, 4-heptylphenyl acrylate, 4-octylphenyl acrylate, 4-decylphenyl acrylate, 4-dodecylphenyl acrylate, 4-hexylphenyl methacrylate, 4-heptyl Phenyl methacrylate, 4-octylphenyl methacrylate, 4-decylphenyl methacrylate, 4-dodecylphenyl methacrylate, 4-hexyloxyphenyl acrylate, 4-heptyloxyphenyl acrylate, 4-octyloxy Phenyl acrylate, 4-nonyloxyphenyl acrylate, 4-decyloxyphenyl acrylate, 4-dodecyloxyphenyl acrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxyphenyl methacrylate, 4-octyl Oxyphenyl methacrylate, 4-nonyloxyphenyl methacrylate, 4-decyloxyphenyl methacrylate, 4-dodecyloxyphenyl methacrylate, 4-hexylcyclohexyl acrylate, 4-heptylcyclohexyl acryl Late, 4-octyl Lohexyl acrylate, 4-nonylcyclohexyl acrylate, 4-decylcyclohexyl acrylate, 4-dodecylcyclohexyl acrylate, 4-hexylcyclohexyl methacrylate, 4-heptylcyclohexyl methacrylate, 4-octylcyclohexyl methacrylate, 4-nonylcyclohexyl methacrylate, 4-decylcyclohexyl methacrylate, 4-dodecylcyclohexyl methacrylate, 4-hexyloxycyclohexyl acrylate, 4-heptyl Oxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, 4-nonyloxycyclohexyl acrylate, 4-decyloxycyclohexyl acrylate, 4-dodecyloxycyclohexyl acrylate, 4-hexyloxycyclohexyl meta Acrylate, 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decyloxycyclohexyl methacrylate Methacrylate and 4-dodecyloxycyclohexyl methacrylate are mentioned. Among these compounds, 4-n-hexyloxyphenyl acrylate, 4-n-octyloxyphenyl acrylate, 4-n-decyloxyphenyl acrylate, 4-n-dodecyloxyphenyl acrylate, 4-n-hexa Decyloxyphenyl acrylate, 4-n-octadecyloxyphenyl acrylate, 4-n-hexyloxyphenyl methacrylate, 4-n-octyloxyphenyl methacrylate, 4-n-decyloxyphenyl methacrylate, 4-n-dodecyloxyphenyl methacrylate, 4-n-hexadecyloxyphenyl methacrylate and 4-n-octadecyloxyphenyl methacrylate are preferable.                     

The compound of the present invention is, for example, a compound in which Y ² is an ester bond in the formula (1) is prepared by an esterification reaction using a carboxylic acid or derivative thereof having an ethylenically unsaturated double bond and an alcohol or a derivative thereof. can do.

[Carboxylic acids or derivatives thereof having ethylenically unsaturated double bonds]

As carboxylic acid which has ethylenically unsaturated double bond, acrylic acid, methacrylic acid, cinnamic acid, etc. are mentioned, for example. As the derivative of the carboxylic acid, halides and alkali metal salts can be used, for example. Examples of the halogen include fluorine, chlorine and bromine. Moreover, sodium, potassium etc. are mentioned as an alkali metal, for example.

[Alcohol or Derivatives thereof]

Examples of the alcohol include cyclohexyl alcohol, bicyclohexyl alcohol substituted with a linear or branched alkyl group having 1 to 30 carbon atoms, and phenol, biphenol, naphthol, and terphenol substituted with the alkyl group as described above. The alkyl group of these compounds may be substituted with an alkoxyl group having 1 to 10 carbon atoms, a halogen atom or a phenyl group, and its cyclic skeleton may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogen atom or a phenyl group You may be.

Moreover, a halide is mentioned as an alcohol derivative, for example. As a halide, a chloride, bromide, and iodide are mentioned, for example.

Synthesis of Compound of the Invention                     

The use ratio of (meth) acrylic acid or a derivative thereof and alcohol provided in the synthesis reaction of (meth) acrylic acid is preferably a ratio such that (meth) acrylic acid or a derivative thereof is 1 to 2 equivalents to 1 equivalent of the hydroxyl group contained in the alcohol. More preferably, it is the ratio which becomes 1.2 to 1.5 equivalent. Examples of the (meth) acrylic acid derivative that can be used include (meth) acrylic acid, alkali metal salts of (meth) acrylic acid, and halogenated (meth) acryloyl.

Synthetic reaction of the (meth) acrylic acid ester may use a conventional esterification reaction, a method of dehydrating and condensing carboxylic acid and alcohol using an acid catalyst or a base catalyst, reaction of carboxylic acid halides with alcohol, carboxyl The reaction of an alkali metal salt of an acid with a halide can be used. Reaction temperature becomes like this. Preferably it is carried out on the temperature conditions of -20-150 degreeC, More preferably, it is 0-100 degreeC. The reaction solvent is not particularly limited as long as it is other than alcohol, primary and secondary amines, and is capable of dissolving the synthesized (meth) acrylic acid ester and starting material. For example, diethyl ether, tetrahydrofuran, dichloro Methane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, N-methyl-2-pyrrolidone, N, N-dimethylacet Amide, N, N-dimethylformamide, dimethyl sulfoxide and γ-butyrolactone.

In addition, it is preferable that the usage-amount of an organic solvent is an amount such that the alcohol used as a starting material will be 0.1-20 weight% with respect to whole quantity of the reaction solution, ie, the total usage-amount of an organic solvent and alcohol.

Here, in order to prevent superposition | polymerization in reaction, you may use a polymerization inhibitor in the range which does not inhibit reaction.

Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, N-nitrosophenylhydroxyamine aluminum salt, p-tertiary-butylcatechol, 2,4-dinitrophenol, and the like.

In this way, a crude product of (meth) acrylate is obtained. This reaction product can be purified by recrystallization, distillation or chromatography to obtain the compound of the present invention.

[Laminated liquid crystal aligning film and liquid crystal display element containing this]

The laminated liquid crystal aligning film obtained using the compound of this invention and the liquid crystal display element containing this can be manufactured by the following method, for example.

Protruding structures formed of organic materials are formed on one or both surfaces of the substrate on which the patterned transparent conductive film is provided. When the projecting structure is formed only on one side of the substrate, the transparent conductive film on the other side of the substrate needs to have a slit pattern. In addition, when not forming a protrusion structure, you may pattern the transparent conductive film on both surfaces of a board | substrate to slit shape. It is preferable that it can be patterned as an organic material which comprises a protrusion structure, and a photoresist material is preferable at this point. In addition, the use of a positive resist is easy to control the shape of the protruding structure and is preferable in view of orientation control. Examples of the positive resist to be used include novolak resins and acrylate resins. Moreover, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. The transparent conductive film provided on one side of the substrate includes, for example, an NESA film (registered trademark of PPG Co., Ltd.) containing tin oxide (SnO ₂ ) and indium tin oxide (In ₂ O ₃ -SnO ₂ ). ITO membrane, etc. can be used. The photoetching method and the method of using a mask beforehand are used for patterning such a transparent conductive film. The coating film is formed by apply | coating the liquid crystal aligning agent containing polyimide, polyamic acid, etc. by the method of a roll coater method, a spinner method, a printing method, etc. on the board | substrate with which protrusion was formed, and then heating a coating surface. can do. When apply | coating a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. The heating temperature after liquid crystal aligning agent application becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Moreover, when a liquid crystal aligning agent contains a polyamic acid, the film | membrane used as the 1st liquid crystal aligning film which is a 1st layer of a multilayer film containing polyimide etc. can be formed by removing an organic solvent after application | coating, and further heating this advances dehydration ring closure. It is also possible to form an imidized coating film. The film thickness of the formed coating film is 100-5,000 Pa, Preferably it is 200-1,000 Pa.

As mentioned above, two board | substrates with which the 1st liquid crystal aligning film was formed are produced, two board | substrates are opposingly arranged through a gap (cell gap), and two board | substrate peripheral parts are bonded together using a sealing agent.

As the sealant, for example, a thermosetting agent or a photosensitive curing agent or an epoxy resin containing aluminum oxide spheres as a spacer can be used.

The liquid crystal and the compound of the present invention are injected and filled into the cell gap partitioned by the substrate surface and the sealing agent, and the injection hole is sealed to form a liquid crystal cell.

As a liquid crystal which can be used, a nematic liquid crystal and a smectic liquid crystal are mentioned, for example. Especially, a nematic type liquid crystal is preferable, For example, a siphonbase type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystal, a dioxane type liquid crystal, a bicyclo octane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, such liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck Co., Ltd.). The chiral agent etc. which are sold can also be added and used. Ferroelectric liquid crystals such as o-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

After mixing the compound of this invention with these liquid crystals, and inject | pouring into a liquid crystal cell as mentioned above, by irradiating a radiation, the compound of this invention superposes | polymerizes and a polymer is formed as a 2nd liquid crystal aligning film on a 1st liquid crystal aligning film, and a laminated alignment film is formed. It can manufacture.

The concentration before light irradiation of the compound of the present invention in the liquid crystal is, for example, 5% by weight or less, preferably 3% by weight or less, more preferably 1.5% by weight or less. When the concentration exceeds 5% by weight, scattering of transmitted light is caused after polymerization, so that it is difficult to obtain a good image.

As a radiation which superposes | polymerizes the compound of this invention, visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays, etc. can be used, for example. Radiation having a wavelength in the range of 150 nm to 800 nm is preferred, and especially radiation having a wavelength of 240 nm to 500 nm.

As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.

As an exposure amount, 0.01-50 J / cm <^2> is preferable, for example, and 0.1-20 J / cm <^2> is more preferable. Moreover, it is preferable to expose by the temperature which the liquid crystal to be used shows a liquid crystal phase.

And a liquid crystal display element is obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell so that the polarization direction may orthogonally cross.

As a polarizing plate joined to the outer surface of a liquid crystal cell, the polarizing plate called H film which absorbed iodine while extending | stretching polyvinyl alcohol, and the polarizing plate which interposed between the cellulose acetate protective film or the H film itself is mentioned.                     

<Examples>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

[Film thickness of second layer of laminated alignment film]

By disassembling the liquid crystal display element, scratching the alignment film with a cutter to expose the substrate surface, and measuring the generated step with a contact film thickness meter, the film thickness of the stacked alignment film (the film thickness of the first layer is 800 kPa) Measured.

The film thickness of the 2nd layer derived from the polymeric compound of this invention was computed by following formula (1).

(Film thickness of the second layer) = (film thickness of the laminated alignment film)-800

[Orientation of Liquid Crystal]

The presence or absence of the abnormal domain at the time of turning on and off the voltage to a liquid crystal display element was observed with the polarization microscope, and the case where there was no abnormal domain was judged as "good".

[Voltage retention rate]

When the voltage of 5 V was applied to the liquid crystal display element at room temperature with 60 microseconds of application time and 167 milliseconds of span, the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica Co., Ltd.

(Residual DC voltage)

A 30 Hz, 2.0 V square wave superimposed on a liquid crystal display element at 1.0 ° C. was applied at an environmental temperature of 70 ° C. for 1 hour to flicker the voltage remaining in the liquid crystal cell immediately after the DC voltage was cut off. The residual DC voltage was obtained by the erasure method.

&Lt; Example 1 >

10 g of 4-n-hexyloxyphenol and 200 mL of dehydrated tetrahydrofuran were added to a 500-neck three-necked flask equipped with a silica gel drying tube, followed by stirring, followed by addition of 35 mg of hydroquinone monomethyl ether, followed by triethylamine 6 g was added and stirred at room temperature to dissolve. 6 g of acryloyl chloride was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 2 hours.

The reaction solution was washed with 10% K ₂ CO ₃ aqueous solution, saturated brine and water in that order, dried over magnesium sulfate, and then the solvent was distilled off.

The obtained liquid was purified by column chromatography to obtain 10.5 g of 4-n-hexyloxyphenyl acrylate with high purity.

The results of NMR (nuclear magnetic resonance) measurement are shown in FIG. 1 and the following.

¹ H-NMR (CDCl ₃ , δm): 0.8-2.0 (11H, m), 3.9 (2H, t), 5.9-7.2 (7H, m)

<Example 2>

Except having used 4-n-octyloxyphenol and acryloyl chloride in Example 1, 10.1 g of 4-n-octyloxyphenyl acrylates were obtained by the same method with high purity.

The NMR measurement results are shown in FIG. 2 and below.

¹ H-NMR (CDCl ₃ , δm): 0.9-2.0 (15H, m), 3.9 (2H, t), 5.9-7.2 (7H, m)

&Lt; Reference Example 1 &

(1) Preparation of Liquid Crystal Mixture

10 mg of the specific compound obtained in Example 1 and 10 mg of dimethylol-tricyclodecane diacrylate were dissolved in 1 g of a negative liquid crystal MLC-6608 (manufactured by Merck Co., Ltd.) to form a mixture.

(2) Preparation of liquid crystal aligning agent

9.7 g (90 mmol) of p-phenylenediamine and 5.2 g (10 mmol) of cholesteryl 3,5-diaminobenzoate are dissolved in 200 ml of 1-methyl-2-pyrrolidone, and 2,3 6.7 g (30 mmol) of and 5-tricarboxycyclopentyl acetic dianhydride and 15 g (70 mmol) of pyromellitic dianhydride were added, and reaction was performed at 60 degreeC for 6 hours. Thereafter, the reaction solution was poured into 5,000 ml of methanol to obtain a white precipitate, which was dried at room temperature under reduced pressure to obtain a white poly having an intrinsic viscosity of 1.0 dl / g (25 ° C in 1-methyl-2-pyrrolidone). Amic acid powder was obtained. This polyamic acid powder was dissolved in 1-methyl-2-pyrrolidone to obtain a liquid crystal aligning agent having a solid content concentration of 3%.

(3) Preparation of Liquid Crystal Display Element

[1] A liquid crystal aligning agent prepared in (2) is applied by spin coating on a transparent conductive film substrate including an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by baking at 180 ° C. for 1 hour. A coating film having a dry film thickness of 800 kPa was formed.

[2] As described above, two substrates having a liquid crystal alignment film were formed, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5 μm was applied to the outer edge of each substrate by screen printing. Two board | substrates were opposingly arranged through the clearance gap, the outer edge part contacted and crimped | bonded, and the adhesive agent was hardened.

[3] A mixture of nematic liquid crystal "MLC-6608" (manufactured by Merck Co., Ltd.) manufactured as described above is injected and filled into the cell gap partitioned by the adhesive of the outer surface and the substrate, and then the injection hole is epoxy-filled. The liquid crystal cell was formed by sealing with a system adhesive. Ultraviolet light containing light having a wavelength of 365 nm, 405 nm, and 436 nm was irradiated to the liquid crystal display element through a photomask at 10 J / cm ² to polymerize a specific compound in the liquid crystal. Then, the liquid crystal display element was manufactured by bonding a polarizing plate to the outer surface of a liquid crystal cell.

[4] About the liquid crystal display device manufactured as described above, the film thickness, vertical alignment property, voltage retention and residual DC voltage of the second layer were evaluated. The results obtained are shown in Table 1 below.

<Reference Example 2>

A liquid crystal mixture was prepared in the same manner as in Reference Example 1 except that the compound obtained in Example 2 was used. Subsequently, using each of the liquid crystal mixtures produced in this manner, a liquid crystal display device was manufactured in the same manner as in Reference Example 1. Each of the produced liquid crystal display elements was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

<Comparative Reference Example 1>

A liquid crystal display device was manufactured in the same manner as in Reference Example 1 except that a liquid crystal containing no compound of the present invention was used. The prepared liquid crystal display device was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

According to the present invention, it is possible to provide a polymerizable compound useful for assisting the vertical alignment and providing a high voltage retention and a low residual type liquid crystal display device.

The liquid crystal display element provided with the liquid crystal aligning film obtained using such a polymeric compound is excellent also in the orientation and reliability of a liquid crystal, and can be effectively used for various apparatuses, For example, a table calculator, a wristwatch, a table clock, a counting plate, It can be used suitably as display apparatuses, such as a word processor, a personal computer, and a liquid crystal television.

Claims (8)

Polymeric compound represented by following formula (1). <Formula 1> RY ¹ -AY ² -Z (Wherein R is a linear alkyl group having 6 to 30 carbon atoms, A is a phenylene group, Y ¹ is an ether bond, Y ² is an ester bond, and Z is an ethenyl group or 1-methylethenyl group, provided that A phenylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogen atom or a phenyl group.) The polymerizable compound according to claim 1, wherein R is a linear alkyl group having 6 to 20 carbon atoms. The polymerizable compound according to claim 1 or 2, which is used for producing a laminated alignment film. The polymeric compound of Claim 1 or 2 containing a liquid crystal, The mixture characterized by the above-mentioned. The mixture of claim 4 further comprising di (meth) acrylate. The mixture of claim 5 wherein said di (meth) acrylate is dimethylol-tricyclodecane diacrylate. The mixture according to claim 4, wherein the liquid crystal is a nematic liquid crystal. The mixture of Claim 4 is filled between two board | substrates with which the 1st liquid crystal aligning film was formed, and then it irradiates and polymerizes the polymeric compound in the said mixture, and forms a 2nd liquid crystal aligning film on the said 1st liquid crystal aligning film, and is laminated | stacked. The manufacturing method of the liquid crystal display element characterized by including the process of manufacturing an oriented film.

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