KR101021705B1 - Liquid Crystal Alignment Film and Process for Preparing the Same - Google Patents

Abstract

This invention provides the liquid crystal aligning film which can manufacture the liquid crystal display element with high contrast, high voltage retention, and low residual DC voltage, and its manufacturing method.

In addition, the present invention encloses a compound having a liquid crystal and an ethylenically unsaturated bond and a compound having a hydrophobic group between two sandwiched substrates in which a polyamic acid and a polyimide film are present on the surface in contact with the liquid crystal of the substrate, followed by irradiation or The method of manufacturing a liquid crystal aligning film by heating and superposing | polymerizing the said compound on the said polyamic acid or a polyimide film, and the liquid crystal aligning film which are obtained laminated bodies are provided.

Liquid crystal aligning film, liquid crystal display element, contrast, voltage retention, residual DC voltage, polyamic acid, polyimide film

Description

Liquid Crystal Alignment Film and Process for Preparing the Same

This invention relates to the liquid crystal aligning film comprised by the laminated body, and its manufacturing method. More specifically, the present invention relates to a liquid crystal aligning film and a method of manufacturing the same, which assist the alignment control by the liquid crystal aligning film in the liquid crystal display device and enable the production of a liquid crystal display device panel having a high voltage retention and a low residual DC voltage.

At present, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the said surface of the board | substrate with which the transparent conductive film is provided, and it forms the board | substrate for liquid crystal display elements, and arranges the two sheets facing each other, and the clearance gap between them. The so-called TN type (Twisted Nematic), in which a nematic liquid crystal layer having positive 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 liquid crystal cell 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 the birefringence generated when the major axis of the liquid crystal molecule is continuously twisted over 180 degrees between the substrates. To use the 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 the "remaining DC voltage") is 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.

This invention is made | formed based on the above circumstances, The objective of this invention is providing the liquid crystal aligning film which can manufacture the liquid crystal display element with high contrast, high voltage retention, and low residual DC voltage.

Another object of the present invention is to provide a method for producing the liquid crystal alignment film.

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

According to this invention, the said objective and advantage of this invention are achieved by the liquid crystal aligning film which is a laminated body first.

According to the present invention, the above object and advantage of the present invention is that a group having a liquid crystal and an ethylenically unsaturated bond between the two sandwiched substrates in which a film of polyamic acid and polyimide is present on the surface in contact with the liquid crystal of the substrate, A compound having a hydrophobic group is encapsulated, and then irradiated or heated to polymerize the compound on the polyamic acid or polyimide film, thereby achieving a liquid crystal alignment film production method.

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

[Liquid crystal aligning film composed of laminated body]

The liquid crystal alignment film constituted by the laminate has a hydrophobic group and a group having an ethylenically unsaturated bond and a first film containing at least one member selected from polyamic acid and polyimide (hereinafter referred to as "polyamic acid, etc."). It is composed of a second membrane comprising a polymer of a compound (hereinafter referred to as "specific compound").

The 1st film which is a 1st layer can be formed using a normal liquid crystal aligning agent for liquid crystal aligning film formation. Its film thickness is preferably 100 to 5,000 mm 3, more preferably 200 to 1000 mm 3.

Polyamic acid etc. can be synthesize | combined by a conventional method using tetracarboxylic dianhydride and diamine (refer Unexamined-Japanese-Patent No. 2001-311080).

The 2nd film which is a 2nd layer can be formed by superposing | polymerizing a specific compound in presence of a liquid crystal in the panel of a liquid crystal display element. The film thickness thereof is preferably 10 to 2,000 mm 3, more preferably 50 to 1,000 mm 3, still more preferably 50 to 700 mm 3.

Certain compounds have a hydrophobic group and a group having an ethylenically unsaturated bond as described above. As group which has ethylenically unsaturated bond, a (meth) acryloyloxy group is mentioned as a preferable thing, for example. Hydrophobic groups include monovalent and cyclohexylene groups, bicyclohexylene groups, phenylene groups, biphenylene groups, daphenylene groups, naphthylene groups such as linear or branched alkyl groups having 6 to 40 carbon atoms, or alicyclic groups. Bivalent groups are mentioned. Such a group may have substituents, such as an alkyl group, an alkoxyl group, a halogen group, and a phenyl group.

As a specific example of a specific compound, the compound represented by following formula (1) is mentioned.

RY ^1- (AY ² ) _n -Z

In formula, R is a C1-C40 linear or branched alkyl group, or an alicyclic group, A is a C1-C10 alkylene group, a cyclohexylene group, a bicyclohexylene group, a phenylene group, a biphenylene group, A diphenylene group and a naphthalene group, and a divalent organic group selected from the following chemical formulas, Y ¹ and Y ² independently of each other are a bonding group selected from a single bond, an ether bond, an ester bond, an amide bond, and Z is an ethylenically unsaturated It is a polymeric functional group containing a bond, n is an integer of 0-3. However, the said alkyl group of R may be substituted with a C1-C10 alkoxyl group, a hydroxyl group, a halogen atom, or a phenyl group, and the said alicyclic group of R and the divalent organic group of A may be a C1-C10 alkyl group, C1-C10 10 may be substituted with an alkoxyl group, a hydroxyl group, a halogen atom or a phenyl group.

As R, a C4-C40 linear or branched alkyl group is preferable, and as A, a cyclohexylene group, a bicyclohexylene group, a phenylene group, a biphenylene group, or the said chemical formula is preferable.

Moreover, as Y <^1> , a single bond or an ether bond or ester bond is preferable, and as Y <^2> , an ester bond is more preferable. Moreover, as Z, an ethenyl group and 1-methylethenyl group are preferable. As the group represented by ZY ^2-, acryloyl group and methacryloyl group are particularly preferable.

As a specific compound represented by the said Formula (1), for example, 2-butylphenyl acrylate, 2-pentylphenyl acrylate, 2-hexylphenyl acrylate, 2-heptylphenyl acrylate, 2-octylphenyl acrylate, 2 Nonylphenyl acrylate, 2-decylphenyl acrylate, 2-dodecylphenyl acrylate, 2-hexadecylphenyl acrylate, 2-octadecylphenyl acrylate, 2-butylphenyl methacrylate, 2-pentylphenyl meta Acrylate, 2-hexylphenyl methacrylate, 2-heptylphenyl methacrylate, 2-octylphenyl methacrylate, 2-nonylphenyl methacrylate, 2-decylphenyl methacrylate, 2-dodecylphenyl methacrylate Latex, 2-hexadecylphenyl methacrylate, 2-octadecylphenyl methacrylate, 2-butyloxyphenyl acrylate, 2-pentyloxyphenyl acrylate, 2-hexyloxyphenyl acrylate, 2-heptyloxyphenyl acrylic Rate, 2-octyloxyphenyl acrylate, 2-nonyloxyphenyl acrylate, 2-decyloxyphenyl acrylate, 2-dodecyloxyphenyl acrylate, 2-hexadecyloxyphenyl acrylate, 2-octadecyloxyphenyl acrylate , 2-butyloxyphenyl methacrylate, 2-pentyloxyphenyl methacrylate, 2-hexyloxyphenyl methacrylate, 2-heptyloxyphenyl methacrylate, 2-octyloxyphenyl methacrylate, 2-nonyloxy Phenyl methacrylate, 2-decyloxyphenyl methacrylate, 2-dodecyloxyphenyl methacrylate, 2-hexadecyloxyphenyl methacrylate, 2-octadecyloxyphenyl methacrylate, 2-butylcyclohexyl acrylic Latex, 2-pentylcyclohexyl acrylate, 2-hexylcyclohexyl acrylate, 2-heptylcyclohexyl acrylate, 2-octylcyclohexyl acrylate, 2-nonylcyclohexyl acrylate, 2-decylcyclo Sil acrylate, 2-dodecylcyclohexyl acrylate, 2-hexadecylcyclohexyl acrylate, 2-octadecylcyclohexyl acrylate, 2-butylcyclohexyl methacrylate, 2-pentylcyclohexyl methacrylate , 2-hexylcyclohexyl methacrylate, 2-heptylcyclohexyl methacrylate, 2-octylcyclohexyl methacrylate, 2-nonylcyclohexyl methacrylate, 2-decylcyclohexyl methacrylate, 2- Dodecylcyclohexyl methacrylate, 2-hexadecylcyclohexyl methacrylate, 2-octadecylcyclohexyl methacrylate, 2-butyloxycyclohexyl acrylate, 2-pentyloxycyclohexyl acrylate, 2- Hexyloxycyclohexyl acrylate, 2-heptyloxycyclohexyl acrylate, 2-octyloxycyclohexyl acrylate, 2-nonyloxycyclohexyl acrylate, 2-decyloxycyclohexyl acrylate 2, 2-dodecyloxycyclohexyl acrylate, 2-hexadecyloxycyclohexyl acrylate, 2-octadecyloxycyclohexyl acrylate, 2-butyloxycyclohexyl methacrylate, 2-pentyloxycyclohexyl methacrylate Latex, 2-hexyloxycyclohexyl methacrylate, 2-heptyloxycyclohexyl methacrylate, 2-octyloxycyclohexyl methacrylate, 2-nonyloxycyclohexyl methacrylate, 2-decyloxycyclohexyl methacrylate Late, 2-dodecyloxycyclohexyl methacrylate, 2-hexadecyloxycyclohexyl methacrylate, 2-octadecyloxycyclohexyl methacrylate,

3-butylphenyl acrylate, 3-pentylphenyl acrylate, 3-hexylphenyl acrylate, 3-heptylphenyl acrylate, 3-octylphenyl acrylate, 3-nonylphenyl acrylate, 3-decylphenyl acrylate, 3 -Dodecylphenyl acrylate, 3-hexadecylphenyl acrylate, 3-octadecylphenyl acrylate, 3-butylphenyl methacrylate, 3-pentylphenyl methacrylate, 3-hexylphenyl methacrylate, 3-heptyl Phenyl methacrylate, 3-octylphenyl methacrylate, 3-nonylphenyl methacrylate, 3-decylphenyl methacrylate, 3-degree decylphenyl methacrylate, 3-hexadecylphenyl methacrylate, 3-octa Decylphenyl methacrylate, 3-butyloxyphenyl acrylate, 3-pentyloxyphenyl acrylate, 3-hexyloxyphenyl acrylate, 3-heptyloxyphenyl acrylate, 3-octyloxyphenyl acrylate, 3-nonyloxy Phenyl acryl , 3-decyloxyphenyl acrylate, 3-dodecyloxyphenyl acrylate, 3-hexadecyloxyphenyl acrylate, 3-octadecyloxyphenyl acrylate, 3-butyloxyphenyl methacrylate, 3-pentyloxy Phenyl methacrylate, 3-hexyloxyphenyl methacrylate, 3-heptyloxyphenyl methacrylate, 3-octyloxyphenyl methacrylate, 3-nonyloxyphenyl methacrylate, 3-decyloxyphenyl methacrylate, 3-dodecyloxyphenyl methacrylate, 3-hexadecyloxyphenyl methacrylate, 3-octadecyloxyphenyl methacrylate, 3-butylcyclohexyl acrylate, 3-pentylcyclohexyl acrylate, 3-hexyl Clohexyl acrylate, 3-heptylcyclohexyl acrylate, 3-octylcyclohexyl acrylate, 3-nonylcyclohexyl acrylate, 3-decylcyclohexyl acrylate, 3-dodecylcyclohexyl acrylate, 3- Sardecylcyclohexyl acrylate, 3-octadecylcyclohexyl acrylate, 3-butylcyclohexyl methacrylate, 3-pentylcyclohexyl methacrylate, 3-hexylcyclohexyl methacrylate, 3-heptylcyclohexyl Methacrylate, 3-octylcyclohexyl methacrylate, 3-nonylcyclohexyl methacrylate, 3-decylcyclohexyl methacrylate, 3-dodecylcyclohexyl methacrylate, 3-hexadecylcyclohexyl meta Acrylate, 3-octadecylcyclohexyl methacrylate, 3-butyloxycyclohexyl acrylate, 3-pentyloxycyclohexyl acrylate, 3-hexyloxycyclohexyl acrylate, 3-heptyloxycyclohexyl acrylate, 3-octyloxycyclohexyl acrylate, 3-nonyloxycyclohexyl acrylate, 3-decyloxycyclohexyl acrylate, 3-dodecyloxycyclohexyl acrylate, 3-hexadecyl Cycyclohexyl acrylate, 3-octadecyloxycyclohexyl acrylate, 3-butyloxycyclohexyl methacrylate, 3-pentyloxycyclohexyl methacrylate, 3-hexyloxycyclohexyl methacrylate, 3-heptyloxy Cyclohexyl methacrylate, 3-octyloxycyclohexyl methacrylate, 3-nonyloxycyclohexyl methacrylate, 3-decyloxycyclohexyl methacrylate, 3-dodecyloxycyclohexyl methacrylate, 3-hexa Decyloxycyclohexyl methacrylate, 3-octadecyloxycyclohexyl methacrylate,

4-butylphenyl acrylate, 4-pentylphenyl acrylate, 4-hexylphenyl acrylate, 4-heptylphenyl acrylate, 4-octylphenyl acrylate, 4-nonylphenyl acrylate, 4-decylphenyl acrylate, 4 Dodecylphenyl acrylate, 4-hexadecylphenyl acrylate, 4-octadecylphenyl acrylate, 4-butylphenyl methacrylate, 4-pentylphenyl methacrylate, 4-hexylphenyl methacrylate, 4-heptyl Phenyl methacrylate, 4-octylphenyl methacrylate, 4-nonylphenyl methacrylate, 4-decylphenyl methacrylate, 4-dodecylphenyl methacrylate, 4-hexadecylphenyl methacrylate, 4-octa Decylphenyl methacrylate, 4-butyloxyphenyl acrylate, 4-pentyloxyphenyl acrylate, 4-hexyloxyphenyl acrylate, 4-heptyloxyphenyl acrylate, 4-octyloxyphenyl acrylate, 4-nonyloxy Phenyl acryl Agent, 4-dodecyl oxyphenyl acrylate, 4-oxyphenyl hexadecyl acrylate, 4-octadecyloxyphenol phenyl acrylate,

4-butyloxyphenyl methacrylate, 4-pentyloxyphenyl methacrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxyphenyl methacrylate, 4-octyloxyphenyl methacrylate, 4-nonyloxy Phenyl methacrylate, 4-decyloxyphenyl methacrylate, 4-dodecyloxyphenyl methacrylate, 4-hexadecyloxyphenyl methacrylate, 4-octadecyloxyphenyl methacrylate, 4-butylcyclohexyl acrylic Latex, 4-pentylcyclohexyl acrylate, 4-hexylcyclohexyl acrylate, 4-heptylcyclohexyl acrylate, 4-octylcyclohexyl acrylate, 4-nonylcyclohexyl acrylate, 4-decylcyclohexyl acrylic 4-dodecylcyclohexyl acrylate, 4-hexadecylcyclohexyl acrylate, 4-octadecylcyclohexyl acrylate, 4-butylcyclohexyl methacrylate, 4-pentylcyclohexyl methacrylate , 4-hexylcyclohexyl methacrylate, 4-heptylcyclohexyl methacrylate, 4-octylcyclohexyl methacrylate, 4-nonylcyclohexyl methacrylate, 4-decylcyclohexyl methacrylate, 4 -Dodecylcyclohexyl methacrylate, 4-hexadecylcyclohexyl methacrylate, 4-octadecylcyclohexyl methacrylate, 4-butyloxycyclohexyl acrylate, 4-pentyloxycyclohexyl acrylate, 4 -Hexyloxycyclohexyl acrylate, 4-heptyloxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, 4-nonyloxycyclohexyl acrylate, 4-decyloxycyclohexyl acrylate, 4-dodecyloxycyclo Hexyl acrylate, 4-hexadecyloxycyclohexyl acrylate, 4-octadecyloxycyclohexyl acrylate, 4-butyloxycyclohexyl methacrylate, 4-pentyloxycyclohexyl meta Acrylate, 4-hexyloxycyclohexyl methacrylate, 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decyloxycyclohexyl methacrylate Acrylate, 4-dodecyloxycyclohexyl methacrylate, 4-hexadecyloxycyclohexyl methacrylate, 4-octadecyloxycyclohexyl methacrylate, 4- (4-butylcyclohexyl) phenyl acrylate, 4- (4-pentylcyclohexyl) phenyl acrylate, 4- (4-hexylcyclohexyl) phenyl acrylate, 4- (4-octylcyclohexyl) phenyl acrylate, 4- (4-decylcyclohexyl) Phenyl acrylate, 4- (4-dodecylcyclohexyl) phenyl acrylate, 4- (4-hexadecylcyclohexyl) phenyl acrylate, 4- (4-octadecylcyclohexyl) phenyl acrylate, 4- (4-butylcyclohexyl) phenyl methacrylate, 4- (4-pentylcyclohexyl) phenyl methyl Acrylate, 4- (4-hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) phenyl methacrylate, 4- (4-decylcyclohexyl) phenyl methacrylate, 4- ( 4-dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecylcyclohexyl) phenyl methacrylate, 4- (4-octadecylcyclohexyl) phenyl methacrylate,

4- (4-butylcyclohexyl) cyclohexyl acrylate, 4- (4-pentylcyclohexyl) cyclohexyl acrylate, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclo Hexyl) cyclohexyl acrylate, 4- (4-decylcyclohexyl) cyclohexyl acrylate, 4- (4-dodecylcyclohexyl) cyclohexyl acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl Acrylate, 4- (4-octadecylcyclohexyl) cyclohexyl acrylate, 4- (4-butylcyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate, 4 -(4-hexylcyclohexyl) cyclohexyl methacrylate, 4- (4-octylcyclohexyl) cyclohexyl methacrylate, 4- (4-decylcyclohexyl) cyclohexyl methacrylate, 4- (4 -Dodecylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl methacrylate, 4- (4-jade Having carried claw cyclohexyl) cyclohexyl methacrylate,

Cholesteryl acrylate, cholesteryl methacrylate, cholesteryl acrylate, cholesteryl methacrylate, 3-dehydroabiethyloxy-2-hydroxypropyl acrylate, 3-dehydroabiethyloxy- 2-hydroxypropyl methacrylate is mentioned as a preferable compound.

Among these compounds, 4-butylphenyl acrylate, 4-pentylphenyl acrylate, 4-hexylphenyl acrylate, 4-heptylphenyl acrylate, 4-octylphenyl acrylate, 4-nonylphenyl acrylate, 4-decylphenyl Acrylate, 4-dodecylphenyl acrylate, 4-hexadecylphenyl acrylate, 4-octadecylphenyl acrylate, 4-butylphenyl methacrylate, 4-pentylphenyl methacrylate, 4-hexylphenyl methacrylate , 4-heptylphenyl methacrylate, 4-octylphenyl methacrylate, 4-nonylphenyl methacrylate, 4-decylphenyl methacrylate, 4-dodecylphenyl methacrylate, 4-hexadecylphenyl methacrylate 4-octadecylphenyl methacrylate, 4-butyloxyphenyl acrylate, 4-pentyloxyphenyl acrylate, 4-hexyloxyphenyl acrylate, 4-heptyloxyphenyl acrylate, 4-octyloxyphenyl acrylate, 4- Nyloxyphenyl acrylate, 4-decyloxyphenyl acrylate, 4-dodecyloxyphenyl acrylate, 4-hexadecyloxyphenyl acrylate, 4-octadecyloxyphenyl acrylate, 4-butyloxyphenyl methacrylate, 4-pentyloxyphenyl methacrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxyphenyl methacrylate, 4-octyloxyphenyl methacrylate, 4-nonyloxyphenyl methacrylate, 4-decyloxyphenyl Methacrylate, 4-dodecyloxyphenyl methacrylate, 4-hexadecyloxyphenyl methacrylate, 4-octadecyloxyphenyl methacrylate, 4-butylcyclohexyl acrylate, 4-pentylcyclohexyl acrylate , 4-hexylcyclohexyl acrylate, 4-heptylcyclohexyl acrylate, 4-octylcyclohexyl acrylate, 4-nonylcyclohexyl acrylate, 4-decylcyclohexyl acrylate, 4-dodecylcyclo Hexyl acrylate, 4-hexadecylcyclohexyl acrylate, 4-octadecylcyclohexyl acrylate, 4-butylcyclohexyl methacrylate, 4-pentylcyclohexyl methacrylate, 4-hexylcyclohexyl methacryl 4-heptylcyclohexyl methacrylate, 4-octylcyclohexyl methacrylate, 4-nonylcyclohexyl methacrylate, 4-decylcyclohexyl methacrylate, 4-dodecylcyclohexyl methacrylate, 4 -Hexadecylcyclohexyl methacrylate, 4-octadecylcyclohexyl methacrylate, 4-butyloxycyclohexyl acrylate, 4-pentyloxycyclohexyl acrylate, 4-hexyloxycyclohexyl acrylate, 4- Heptyloxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, 4-nonyloxycyclohexyl acrylate, 4-decyloxycyclohexyl acrylate, 4-dodecyloxycyclohexyl acyl Relate, 4-hexadecyloxycyclohexyl acrylate, 4-octadecyloxycyclohexyl acrylate, 4-butyloxycyclohexyl methacrylate, 4-pentyloxycyclohexyl methacrylate, 4-hexyloxycyclohexyl meta Acrylate, 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decyloxycyclohexyl methacrylate, 4-dodecyloxycyclohexyl Methacrylate, 4-hexadecyloxycyclohexyl methacrylate, 4-octadecyloxycyclohexyl methacrylate, 4- (4-butylcyclohexyl) phenyl acrylate, 4- (4-pentylcyclohexyl) phenyl acryl Late, 4- (4-hexylcyclohexyl) phenyl acrylate, 4- (4-octylcyclohexyl) phenyl acrylate, 4- (4-decylcyclohexyl) phenyl acrylate, 4- (4-dodecyl Chlorohexyl) phenyl acrylate, 4- (4-hexadecylcyclohexyl) phenyl acrylate, 4- (4-octadecylcyclohexyl) phenyl acrylate, 4- (4-butylcyclohexyl) phenyl methacrylate, 4- (4-pentyl Cyclohexyl) phenyl methacrylate, 4- (4-hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) phenyl methacrylate, 4- (4-decylcyclohexyl) phenyl methacrylate 4- (4-dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecylcyclohexyl) phenyl methacrylate, 4- (4-octadecylcyclohexyl) phenyl methacrylate,

4- (4-butylcyclohexyl) cyclohexyl acrylate, 4- (4-pentylcyclohexyl) cyclohexyl acrylate, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclo Hexyl) cyclohexyl acrylate, 4- (4-decylcyclohexyl) cyclohexyl acrylate, 4- (4-dodecylcyclohexyl) cyclohexyl acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl Acrylate, 4- (4-octadecylcyclohexyl) cyclohexyl acrylate, 4- (4-butylcyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate, 4 -(4-hexylcyclohexyl) cyclohexyl methacrylate, 4- (4-octylcyclohexyl) cyclohexyl methacrylate, 4- (4-decylcyclohexyl) cyclohexyl methacrylate, 4- (4 -Dodecylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl methacrylate, 4- (4-jade Having carried claw cyclohexyl) cyclohexyl methacrylate,

More preferred are cholesteryl acrylate, cholesteryl methacrylate, cholestanyl acrylate, and cholestanyl methacrylate.                     

A specific compound, for example, a compound in which Y ² in the formula (1) is an ester bond is obtained by reacting an alcohol or a halide having a hydrophobic group with (meth) acrylic acid or a derivative thereof.

〔Alcohol〕

As alcohol which has a hydrophobic group, an alkyl alcohol, an alicyclic alcohol, an aromatic alcohol, etc. are mentioned, for example. The alkyl group, alicyclic group, and aromatic group of these compounds may be substituted with, for example, an alkyl group (except for the alkyl group), a phenyl group, an alkoxyl group, a halogen group, and an alkoxycarbonyl group. As such an alcohol, for example, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, hexadecanol, octadecanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol, hexylhexane Ol, bicyclohexanol, decahydro-2-naphthol, cholesterol, cholestanol, phenol, methylphenol, ethylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, cyclohexylphenol, (ethylcyclohexyl) phenol , (Propylcyclohexyl) phenol, (butylcyclohexyl) phenol, (pentylcyclohexyl) phenol, (hexylcyclohexyl) phenol, (octylcyclohexyl) phenol, bicyclohexylphenol, (ethylcyclohexyl) cyclohexanol , (Propylcyclohexyl) cyclohexanol, (butylcyclohexyl) cyclohexanol, (pentylcyclohexyl) cyclohexanol, (hexylcyclohexyl) cyclohexanol, (octylcyclohexyl) cyclohexanol, 4-n -Hexylphenol, 4-n-heptylphenol, 4-n-octylphenol, 4-n-hexyloxyphenol, 4-n-heptyl Ciphenols, 4-n-octyloxyphenols, 4-t-butylphenols, trifluoromethylphenols, 4-fluorophenols, 2,5-difluorophenols, hydroxybiphenyls and naphthols are exemplified as preferred examples. Can be.                     

[Halogenated Alkyl]

The halide is a compound in which the hydroxyl group of the alcohol is substituted with a halogen atom, and examples thereof include chloride, bromide and iodide. As an alkyl group in the case where a halide is a halogenated allyl, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group is mentioned, for example. These alkyl groups may be linear or branched, and may be substituted with an alkoxyl group.

[Synthesis of (meth) acrylic acid ester]

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 in which 1 or 2 equivalents of (meth) acrylic acid or a derivative thereof are based on 1 equivalent of the hydroxyl group contained in the alcohol. More preferably, it is the ratio used as 1.1-1.5 equivalent. As a (meth) acrylic acid derivative, (meth) acrylic acid, the alkali metal salt of (meth) acrylic acid, a halogenated (meth) acryloyl, etc. are mentioned, for example.

For the synthesis of the (meth) acrylic acid ester, a conventional esterification reaction may be used, for example, a method of dehydrating and condensing a carboxylic acid and an alcohol using an acid catalyst or a base catalyst, a reaction of a carboxylic acid halide and an alcohol, The reaction of the carboxylic acid alkali metal salt with the alkyl halide can be used. The reaction is carried out, for example, under temperature conditions of -20 to 150 ° C, preferably 0 to 100 ° C. The reaction solvent is not particularly limited as long as it is other than alcohol, primary and secondary amines and can dissolve the synthesized (meth) acrylic acid ester and starting material. Examples thereof include diethyl ether, tetrahydrofuran and 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, (gamma) -butyrolactone are mentioned.

Moreover, 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 the whole quantity (total usage-amount of an organic solvent and alcohol) of a reaction solution, for example.

Here, in order to prevent superposition | polymerization in reaction, you may add a polymerization inhibitor in the reaction system 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. And this reaction product can be refine | purified by recrystallization, distillation, or chromatography.

[(Meth) acrylic acid ester having plural (meth) acryl groups]

In this invention, you may use together the specific compound and the (meth) acrylic acid ester which has a some (meth) acryl group copolymerizable with a specific compound in the range which does not inhibit the orientation. Such (meth) acrylic acid esters include, for example, diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Free of monohydroxy diacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid Carboxyl group-containing monoesters;

Propane-1,2,3-tricarboxylic acid (tricarbaric acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3 Tricarboxylic acids such as, 4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate Free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxypropyl methacrylate;

Oligoacrylates or oligomethacrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, spiran resins;

Diacrylates or dimethacrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactones, and

Tris (2-acryloyloxyethyl) phosphate, tris (2-methacryloyloxyethyl) phosphate, etc. are mentioned.

[Other polymeric compounds]

The compound which has ethylenically unsaturated double bond other than a (meth) acryl compound can be used together to the extent which does not impair the effect of this invention. As a compound which can be used, a maleimide compound and a styrene compound are mentioned, for example.

[Laminated alignment film, manufacturing method of this alignment film, and liquid crystal display element using the same]

The laminated alignment film of this invention and the liquid crystal display element obtained using 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 projection structure is formed only on one side of the substrate, the 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, when a positive resist is used, the shape of the protruding structure is easy to control, and is also preferable from the viewpoint of orientation control. Examples of the positive resist to be used include novolak resins and acrylate resins. 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. For patterning of such a transparent conductive film, for example, a photo etching method or a method of using a mask in advance is used. On the board | substrate which formed the processus | protrusion, the liquid crystal aligning agent for normal liquid crystal aligning film formation is apply | coated by methods, such as a roll coater method, a spinner method, and a printing method, for example, and a coating film is formed by heating a coating surface subsequently. In the application of this liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like may be applied in advance to the surface of the 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. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film which becomes an oriented film by removing an organic solvent after application | coating, further heating can advance dehydration ring closure, and can also form more imidized coating film. The film thickness of the first film, which is the first layer to be formed, is as described above.

As mentioned above, two board | substrates with a 1st layer were formed, 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 and an epoxy resin containing aluminum oxide spheres as a spacer can be used.

Liquid crystals and a specific compound, optionally optionally (meth) acrylic acid esters having a plurality of (meth) acrylic acid esters are injected and filled into the cell gap partitioned by the substrate surface and the sealant, and the injection holes are sealed to form a liquid crystal cell. .

Examples of the liquid crystals that can be used include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, cif base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, and phenylcyclohexane liquid crystals. , Ester-based liquid crystals, polyphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals, and the like. 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. Furthermore, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used.

After mixing a specific compound and a liquid crystal, and inject | pouring into a liquid crystal display element, a 2nd film which is a 2nd layer is formed on a 1st layer by irradiating a radiation to a liquid crystal display element.

The concentration of the compound having an unsaturated double bond group in the liquid crystal is, for example, 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. If the concentration exceeds 10% by weight, scattering of transmitted light occurs, so that it is difficult to obtain a good image.

As a radiation which superposes | polymerizes a specific compound, 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 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. In addition, the measuring method and evaluation method in the liquid crystal display element manufactured by the following example and the comparative example are as follows.

[Film thickness of second layer of laminated alignment film]

After disassembling the liquid crystal display element and removing the liquid crystal with acetone, the alignment film was scratched to expose the substrate surface, and the resulting step was measured by a contact film thickness meter to measure the film thickness of the laminated alignment film (film of the first layer). Thickness was 800 mm 3).

The film thickness of the 2nd layer derived from a specific compound 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 a voltage of 5 V is applied to a liquid crystal display at room temperature with 60 microseconds of application time and a span of 16.7 milliseconds, the holding voltage of 16.7 milliseconds after the release of 5 V is applied to VHR-1 manufactured by Toyo Technica Co., Ltd. After the measurement, the voltage retention was obtained.

(Residual DC voltage)

A 30 Hz, 3.0 V square wave superimposed on a liquid crystal display device at a temperature of 25 ° C. was applied for 2 hours at an environment temperature of 25 ° C., and the voltage remaining in the liquid crystal cell immediately after the DC voltage was cut off was flickered. The residual DC voltage was obtained by the erasure method.

Synthesis Example 1

To a 500-neck three-necked flask equipped with a silica gel drying tube, 10 g of β-cholestanol and 200 mL of dehydrated tetrahydrofuran were added and stirred, followed by addition of 35 mg of 2-methoxydihydroquinone and 6 g of triethylamine. It stirred by stirring at room temperature. 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 solid was recrystallized from ethanol to obtain 10.5 g of cholestanyl acrylate (hereinafter referred to as "acrylic acid ester compound I") with high purity (yield 92%).

Synthesis Example 2

Except for using methacryloyl chloride instead of acryloyl chloride in Synthesis Example 1, the desired cholestanyl methacrylate (hereinafter referred to as "methacrylic acid ester compound II") was 93% yielded by the same method. Got it.

&Lt; Synthesis Example 3 &

Except having used cholesterol instead of (beta) -cholestanol in the synthesis example 1, the desired cholesteryl acrylate (henceforth "acrylic acid ester compound III") was obtained by the same method as the yield 93%.

&Lt; Synthesis Example 4 &

Except for using cholesterol and methacryloyl chloride in place of β-Nicolestanol and acryloyl chloride in Synthesis Example 1, the desired cholesteryl methacrylate (hereinafter, "methacrylic acid ester compound IV") was "In 95% yield.                     

&Lt; Synthesis Example 5 &

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 4-hexyloxyphenol was used instead of β-cholestanol, and purified by chromatography to obtain the desired hexyloxyphenyl acrylate (hereinafter referred to as “acrylic acid ester compound V”). ", Yielded 93%.

&Lt; Synthesis Example 6 &

Except for using octyloxyphenol instead of 4-hexyloxyphenol in the synthesis example 5, the desired 4-octyloxyphenyl acrylate (henceforth "acrylic acid ester VI") was obtained by the same method as the yield 93%.

Synthesis Example 7

Except for using 4- (4-hexylphenyl) phenol in place of 4-hexyloxyphenol in Synthesis Example 5, the desired 4- (4-hexylphenyl) phenyl acrylate (hereinafter referred to as "acrylic acid ester VII") To yield a yield of 94%.

Synthesis Example 8

Except for using 4- (4-hexylcyclohexyl) phenol instead of 4-hexyloxyphenol in Synthesis Example 5, the desired 4- (4-hexylcyclohexyl) phenyl acrylate (hereinafter, " Acrylic acid ester VIII ") in 92% yield.

&Lt; Example 1 >

(1) Preparation of Liquid Crystal Mixture

A mixture was prepared by dissolving 10 mg of the acrylic acid ester obtained in Synthesis Example 1 and 10 mg of dimethylol-tricyclodecane diacrylate in 1 g of a negative liquid crystal MLC-6608 (manufactured by Merck).

(2) Preparation of liquid crystal aligning agent for first layer formation

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

[2] As described above, two substrates each having a first film as a first layer 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 a screen printing method. After that, two substrates were disposed to face each other through a gap, and the outer edge portions were contacted and pressed to cure the adhesive.

[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 measured. The results are shown in Table 1 below.

<Examples 2 to 8>

According to the prescription shown in Table 1, the liquid crystal mixture was produced like Example 1 using the (meth) acrylic acid ester (II-VIII) obtained by the synthesis examples 2-8. Subsequently, the liquid crystal display element was manufactured like Example 1 using each liquid crystal mixture produced in this way. Each liquid crystal display element thus produced was evaluated in the same manner as in Example 1. The results are shown in Table 1 together.

<Comparative Examples 1 and 2>

According to the prescription shown in Table 1, the liquid crystal display element was produced like Example 1 by the liquid crystal which does not contain the specific compound in this invention. Each liquid crystal display element thus produced was evaluated in the same manner as in Example 1.

Comparative Example 3                     

It evaluated like Example 1 except polymerizing the mixture of a specific compound and a liquid crystal by light irradiation outside the liquid crystal display element, and inject | pouring this into the liquid crystal display element. The results are shown in Table 1 together.

According to the present invention, it is possible to provide a liquid crystal alignment film that assists vertical alignment and provides a high voltage retention and a low afterimage liquid crystal display element.

The liquid crystal aligning film of this invention can be preferably used in order to comprise an MVA type liquid crystal display element and a PVA type liquid crystal display element. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film is excellent also in the orientation and reliability of a liquid crystal, and can be used effectively for various apparatuses, for example, a desk calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer And a display device such as a liquid crystal television.

Claims (4)

A first membrane comprising at least one selected from polyamic acid and polyimide, and Ethylenically unsaturated, selected from the group consisting of cholestanyl acrylate, cholestanyl methacrylate, cholesteryl acrylate, cholesteryl methacrylate, 4-hexyloxyphenyl acrylate and 4-octyloxyphenyl acrylate It is a laminated body which consists of a 2nd film containing the polymer of the group which has a bond, and the compound which has a hydrophobic group, The liquid crystal aligning film which contacts with a liquid crystal at the said 2nd film side. Liquid crystal and cholestanyl acrylate, cholestanyl methacrylate, cholester between two sandwiched substrates in which a film containing at least one selected from polyamic acid and polyimide is present on the surface in contact with the liquid crystal of the substrate. Encapsulating a compound having an ethylenically unsaturated bond and a compound having a hydrophobic group selected from the group consisting of reyl acrylate, cholesteryl methacrylate, 4-hexyloxyphenyl acrylate and 4-octyloxyphenyl acrylate, and then irradiating Or heating to polymerize the compound on the polyamic acid or polyimide film. delete delete