JP5071644B2 - Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a novel polyorganosiloxane, a liquid crystal alignment film, and a liquid crystal display element. More specifically, a polyorganosiloxane used for forming a liquid crystal alignment film capable of imparting liquid crystal alignment ability by irradiation with polarized or non-polarized radiation without rubbing, such a liquid crystal alignment film, and The present invention relates to a liquid crystal display element having such a liquid crystal alignment film.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates as necessary. Liquid crystal display elements having liquid crystal cells such as TN (twisted nematic), STN (super twisted nematic), and IPS (in-plane switching) are known (see Patent Documents 1 and 2). .
In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align the liquid crystal in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, if the liquid crystal alignment film is formed by rubbing, dust is likely to be generated in the process or static electricity is likely to be generated, so that dust adheres to the alignment film surface and causes display defects. There was a problem. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Further, in liquid crystal display elements that will be further refined in the future, unevenness occurs on the surface of the substrate as the density of pixels increases, so that uniform rubbing is a problem.
As another means of aligning the liquid crystal in the liquid crystal cell, the liquid crystal aligning ability is imparted by irradiating the photosensitive thin film made of polyvinyl cinnamate, polyimide, azobenzene derivative or the like with polarized or non-polarized radiation on the substrate surface. A photo-alignment method is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13).

By the way, in a liquid crystal cell of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, etc., the liquid crystal alignment film needs to have a pretilt angle characteristic that tilts and aligns liquid crystal molecules at a predetermined angle with respect to the substrate surface. is there. In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by tilting the incident direction of the irradiated radiation to the substrate surface from the substrate normal.
Further, as an operation mode of a liquid crystal display element different from the above, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules must be tilted from the substrate normal direction to one direction in the substrate surface. There is. As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A method of tilting (pretilting) has been proposed.

The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. That is, it is known that the tilt direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film provided with an alignment regulating force and a pretilt angle by a photo-alignment method (Patent Documents 11 to 12 and 14). ~ 16).
As described above, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, the conventional photo-alignment film has a problem that a large amount of radiation is required to obtain a large pretilt angle. For example, in a photo-alignment film containing an azobenzene derivative, it has been reported that in order to obtain a sufficient pretilt angle, radiation whose optical axis is tilted from the substrate normal must be irradiated at 1 J / cm ² or more. (See Patent Documents 13 to 14 and Non-Patent Document 1).
JP 56-91277 A JP-A-1-120528 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A JP 2002-250924 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A J. et al. of the SID 11/3, 2003 p. 579

  An object of the present invention is to provide a polyorgano, which is used for forming a liquid crystal alignment film that has excellent coating properties and electrical characteristics, and can impart liquid crystal alignment ability by irradiation with polarized or non-polarized radiation without rubbing treatment. It is to provide siloxane and a method for producing the same.

  Another object of the present invention is to provide a liquid crystal alignment film comprising the polyorganosiloxane.

  Still another object of the present invention is to provide a liquid crystal display device.

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

The above objects and advantages of the present invention are as follows.

Here, Z is the later of the repeating unit represented by the following formula I photosensitive groups der cause crosslinking reaction or isomerization reaction by the light of wavelength 200 to 400 nm (2) or (3) the formula (6 1), (6-3) - (6-10) and (6-12) - (6-14) of Ri der any structure represented by each, X is a hydroxyl group, having 1 to 20 carbon atoms An alkyl group, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or X of another repeating unit may form a bridge through —O—.
And having a weight average molecular weight in the range of 1,000 to 100,000 (hereinafter, referred to as the polyorganosiloxane of the present invention).

Here, A ₁ and A ₂ may be the same or different, and are monovalent organic groups including an alkyl group or an alicyclic group which may be substituted with a fluorine atom having 1 to 40 carbon atoms, B ₁ and B ₂ may be the same or different, and are a fluorine atom or a cyano group, p is an integer of 0 to 4, S ₁ and S ₂ may be the same or different, and A divalent organic group having 1 to 20 alkylene groups, X ₁ and X ₂ may be the same or different, and are a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , An alkoxyl group having 1 to 20 carbon atoms, or X of another repeating unit may form a bridge through —O—.

According to the present invention, the above objects and advantages of the present invention, the second, the following equation (4) and the following formula (1 ') a silane compound represented by one of the silane compounds represented by each of (5) There is provided a method for producing the polyorganosiloxane of the present invention by hydrolyzing and condensing at least one selected from the group consisting of:

ここで、Ｚの定義は上記式（１）に同じであり、Ｒ _１ は炭素数１〜２０のアルキル基または炭素数６〜２０のアリール基であり、Ｙ _１ は炭素数１〜２０のアルコキシル基または塩素原子であり、ｎは２または３である。
Here, the definitions of A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S ₂ and p are the same as those in the above formulas (2) and (3), and R ₁ and R ₂ are the same or different. Or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, Y ₁ and Y ₂ may be the same or different, and an alkoxyl group having 1 to 20 carbon atoms or a chlorine atom And n is 2 or 3.

Here, the definition of Z is the same as the above formula (1), R ₁ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ₁ is an alkoxyl having 1 to 20 carbon atoms. A group or a chlorine atom, and n is 2 or 3.

According to the present invention, the above objects and advantages of the present invention, the third, hydrolysis, condensation catalyst is preferably achieved by the production method of polyorganosiloxane is an organic acid.

According to the present invention, the above objects and advantages of the present invention, the fourth, hydrolysis in the presence of a silane compound of the following formula (7), is preferably accomplished by a production method of performing condensation.
Si (R ₃ ) _t (OR ₄ ) _(4-t) (7)
Here, R ₃ is an alkyl group having 1 to 40 carbon atoms which may contain an alicyclic group or an aryl group having 6 to 20 carbon atoms, R ₄ is an alkyl group having 1 to 20 carbon atoms, and t Is 0, 1, 2 or 3.

According to the present invention, the above objects and advantages of the present invention, the fifth, is achieved by a liquid crystal alignment film obtained by irradiation with radiation polarized or unpolarized light to the film formed by the polyorganosiloxane.

According to the present invention, the above objects and advantages of the present invention, the sixth is achieved by a liquid crystal display device having a liquid crystal alignment film.

  According to the present invention, the liquid crystal display element preferably uses a negative liquid crystal.

  When the photo-alignment agent of the present invention is used, a liquid crystal alignment film can be obtained with a smaller radiation dose as compared with the conventional photo-alignment method. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than before. Therefore, these liquid crystal display elements can be effectively applied to various devices, and are suitably used for devices such as a desk calculator, a wristwatch, a table clock, a counter display board, a word processor, a personal computer, or a liquid crystal television.

  Hereinafter, the present invention will be described in detail.

The polyorganosiloxane of the present invention has a repeating unit represented by the formula (1) and has a weight average molecular weight of 1,000 to 100,000.
In formula (1), Z is a photosensitive group that undergoes a crosslinking reaction or an isomerization reaction with light having a wavelength of 200 to 400 nm. X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or other repeating unit X and is bridged through —O—. May be formed.
Preferred X is a group which forms a bridge through —O— together with a hydroxyl group, a methoxy group, an ethoxy group or other repeating unit X.
Preferred examples of the repeating unit represented by the above formula (1) include the repeating unit represented by the above formula (2) or the repeating unit represented by the above formula (3).

In the above formula (2) and the above formula (3), A ₁ and A ₂ may be the same or different, and may be an alkyl group or alicyclic group which may be substituted with a fluorine atom having 1 to 40 carbon atoms. Is a monovalent organic group. B ₁ and B ₂ may be the same or different and are a fluorine atom or a cyano group. p is an integer of 0-4. S ₁ and S ₂ may be the same or different and are a divalent organic group having an alkylene group having 1 to 20 carbon atoms. X ₁ and X ₂ may be the same or different, and may be a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or another repeating unit. A bridge may be formed together with X through —O—.
Specific examples of the group located in the upper side of the silicon atoms in the above formula (2) and (3), for example the formula (6-1), (6-3) - (6-10) and (6-12) The structure represented by each of-(6-14) can be mentioned.

In these formulas, m is an integer of 1 to 20, l is 2m + 1 an integer, k is an integer of from 1 to 10, q is Ri integer der of 2 to 10, m is 3 to 18, l is 3-9 , k is 2-6, q is 2-6 virtuous preferable. Particularly preferably, m is 4 to 10, 1 is 3 to 7, k is 2 to 4, and q is 2 to 4.
The preferred weight average molecular weight of the polyorganosiloxane of the present invention is 1,000 to 50,000.
The polyorganosiloxane of the present invention can be obtained, for example , by hydrolytic condensation of the silane compound represented by the above formula (1 ′) among the silane compounds of the above formula (4) or formula (5).

In formulas (4) and (5), the definitions of A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S ₂ and p are the same as in the above formulas (2) and (3). Examples of Y ₁ and Y ₂ include a chlorine atom and an alkoxyl group such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group and t-butoxy. it can. Of these, a chlorine atom, a methoxy group, and an ethoxy group are preferable.
Examples of R ₁ and R ₂ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-nonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, Examples thereof include alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group, and aryl groups such as phenyl group. Of these, a methyl group, an ethyl group, and a phenyl group are preferable.
Further, n in the formulas (4) and (5) is preferably 3.
Although the compound of Formula (4) can be obtained by a well-known method like the following schemes 1-3, for example, it is not restricted to these methods. However, r in schemes 1 to 3 is k-2. The compound of formula (5) can also be obtained by the same method.

Scheme 1: A compound of formula (4) is obtained by heating, stirring (hydrosilylation reaction) and purifying a precursor of a compound of formula (4) having an alkene and triethoxysilane in the presence of a very small amount of platinum catalyst. Can do.

Scheme 2: A compound of formula (4) by heating and stirring a precursor of a compound of formula (4) having a carboxylic acid and 3-glycidyloxypropyltrimethoxysilane in the presence of a base catalyst such as triethylamine. Can be obtained.

Scheme 3: A compound of formula (4) can be obtained by heating and stirring a compound of formula (4) having a hydroxyl group and triethoxysilanylpropyl-isocyanate in the presence of a tin catalyst such as dibutyltin dilaurate. it can.

Hydrolysis and condensation method of polyorganosiloxane The polyorganosiloxane of the present invention hydrolyzes the silane compound represented by the above formula (1 ′) among the silane compounds represented by the above formula (4) or formula (5), It can be obtained by condensation. At this time, it is preferable to co-hydrolyze and condense the silane compound represented by the formula (7).
In Formula (7), R ₃ is an alkyl group having 1 to 40 carbon atoms which may contain an alicyclic group or an aryl group having 6 to 20 carbon atoms, and R ₄ is an alkyl group having 1 to 20 carbon atoms. And t is 0, 1, 2 or 3.

Examples of the silane compound represented by the formula (7) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- tert-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyl Tri -sec- butoxysilane, ethyltri -tert- butoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane; trimethylmethoxysilane, tri methylethoxy silane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane are preferable.
The silane compound of the formula (7) can be used in an amount of 0 to 100 mol with respect to 1 mol of the silane compound of the formula (4) or the formula (5). It is preferable that it is 1-100 mol. More preferably, it is 2-20 mol.

The hydrolyzed / condensed product can be obtained by reacting a silane compound and water, followed by hydrolysis and partial condensation. In order to hydrolyze and partially condense the silane compound, preferably 1 per mole of siloxane bond (the sum of -Y ₁ of formula (4), -Y _{2 of} formula (5) and OR ₄ of formula (7)). 0.0-1.5 mol of water is used. If the amount of water is 1.0 mol or more, the possibility that the siloxane bond remains unreacted is reduced, there is no possibility that the uniformity of the coating film is lowered, and the storage stability of the liquid crystal aligning agent is lowered. This is preferable because there is less risk of doing so. Water is intermittently or continuously added to the organic solvent in which the silane compound of the present invention is dissolved. At this time, a reaction catalyst can be used. In that case, the catalyst may be added in advance to the organic solvent, or may be dissolved or dispersed in water when water is added. As reaction temperature in this case, Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC.
As the organic solvent, an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent, or an aprotic solvent is preferably used. These can be used alone or in combination of two or more.

Here, examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2- Methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2 -Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl al Lumpur, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohols solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, and polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.
These alcohol solvents may be used alone or in combination of two or more.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- In addition to hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione 2,2,6,6-tetramethyl 3,5-heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like.
These ketone solvents may be used alone or in combination of two or more.

Examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Is mentioned.
These amide solvents may be used alone or in combination of two or more.

Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and acetic acid. i-butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diacetate Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene ether Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate.
These ester solvents may be used alone or in combination of two or more.

Examples of the aprotic solvent include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl- Examples include 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. Of these, polyhydric alcohol solvents, polyhydric alcohol partial ether solvents, and ester solvents are particularly preferred.
In the hydrolysis and partial condensation reaction of the silane compound of the present invention, a catalyst is preferably used. Examples of the catalyst include the following metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy -Tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium,
Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t- Butoxy bis (ethylacetate Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris Titanium chelate compounds such as (ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;
Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonate) zirconium,
Triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) Zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl aceto) Acetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl) Cetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy Tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, Tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Over G) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium chelate compounds such as zirconium;
Examples thereof include aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum.

Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid , Butyric acid, melicic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane. , Diazabicycloundecene, tetramethylammonium hydroxide and the like.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.
The amount of the catalyst used is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the combination of the compound (4), the compound (5) and the compound (7) (in terms of complete hydrolysis condensate). Preferably it is the range of 0.001-1 weight part.
The liquid crystal aligning agent of the present invention is preferably formed by dissolving or dispersing the hydrolysis and condensate in an organic solvent.
As the organic solvent, organic solvents represented by the following formulas (8), (9) and (10) are used.

In Formula (8), R ₃ is hydrogen, a methyl group, an ethyl group or an acetyl group, R ₄ is an alkyl group having 1 to ₄ carbon atoms, and s is an integer of 1 to 3. In formula (9), R ₅ is hydrogen, a methyl group, an ethyl group or an acetyl group, R ₆ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3. In the formula (10), _{R 7} is an alkyl group having 2 to 5 carbon atoms.

As a specific example of the organic solvent represented by the formula (8),
1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, di And propylene glycol dimethyl ether. Of these, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferable.

As a specific example of the organic solvent represented by the formula (9),
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate Butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol and the like. Of these, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), and ethylene glycol monoamyl ether are preferable.

As a specific example of the organic solvent represented by the formula (10),
N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, Examples include 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, and isoamyl acetate. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, and sec-pentyl acetate are preferable.

  Components such as a surfactant may be added to the liquid crystal aligning agent obtained in the present invention. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Furthermore, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant and the like can be mentioned.

  The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy group-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane , 3-Glycidyloxypropylmethyl dimethoxy Silane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxy silane and the like. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4 , And the like as preferred 4'-diaminodiphenylmethane.

The ratio of the polyorganosiloxane that is a reaction product in the liquid crystal aligning agent of the present invention and the solvent is selected in consideration of viscosity, volatility, etc., but the ratio of the polyorganosiloxane in the liquid crystal aligning agent (solid content concentration) ) is a silicon atom contained in the polyorganosiloxane of SiO ₂ concentration in terms of SiO _2, preferably 0.01 to 70 wt%, more preferably from 0.05 to 60 wt%, more preferably 1 to 30% by weight. As will be described later, the liquid crystal aligning agent of the present invention is preferably applied to the substrate surface by, for example, a roll coater method, a spinner method, a printing method, etc., and then heated and dried to form a liquid crystal aligning film. However, when the solid content concentration is less than 0.01% by weight, the film thickness of this coating film may be too small to obtain a good liquid crystal alignment film. Is more than 70% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics. .

Liquid crystal alignment film As a method of forming a liquid crystal alignment film using the liquid crystal aligning agent of this invention, the following method is mentioned, for example. First, the liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with which the transparent conductive film was provided, for example by the roll coater method, the spinner method, the printing method, the inkjet method etc., for example, the temperature of 40-300 degreeC. To form a coating film. At this time, a crosslinking reaction occurs between the polyorganosiloxanes. In order to cause sufficient crosslinking, it is preferable to perform the treatment at 150 to 250 ° C. for 10 minutes to 3 hours. Heating can be performed in air or in nitrogen. The film thickness of the coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm, as a solid content.
As the substrate, for example, a glass such as float glass or soda glass, or a transparent substrate made of a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate can be used.
As the transparent conductive film, for example, a NESA film made of SnO ₂ or an ITO film made of In ₂ O ₃ —SnO ₂ can be used. For patterning these transparent conductive films, a photo-etching method, a method using a mask in advance, or the like is used.
When applying the liquid crystal aligning agent, a functional silane-containing compound or titanate may be applied in advance on the substrate and the transparent conductive film in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film. it can.

Next, the coating film is irradiated with linearly polarized light, partially polarized radiation, or non-polarized radiation, and further subjected to heat treatment at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. As the radiation, ultraviolet rays and visible rays having a wavelength of 200 to 400 nm can be used. When the used radiation is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
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. Further, the ultraviolet rays in the preferable wavelength region can be obtained by means of using a filter, a diffraction grating or the like together with the light source.
The “pretilt angle” in the present invention represents an angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

Liquid crystal display element The liquid crystal display element formed using the liquid crystal aligning agent of this invention is manufactured as follows. A substrate on which the liquid crystal alignment film is formed is prepared, the two sheets are opposed to each other so that the polarization direction of the polarized radiation irradiated on the liquid crystal alignment film is a predetermined angle, and the periphery between the substrates is sealed with a sealant Then, liquid crystal is filled and the filling hole is sealed to constitute a liquid crystal cell. Next, it is desirable that the liquid crystal cell is heated to a temperature at which the liquid crystal used takes an isotropic phase, and then cooled to room temperature to remove the flow alignment at the time of injection.

  Then, the polarizing plates are bonded to both surfaces so that the polarization directions of the polarizing plates form a predetermined angle with the alignment axis of the liquid crystal alignment film of the substrate, respectively, thereby obtaining a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the angle between the polarization directions of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed. Thus, a liquid crystal display element having a TN type or STN type liquid crystal cell can be arbitrarily obtained. On the other hand, in the case where the liquid crystal alignment film is vertically aligned, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, A liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained by bonding the polarization directions so as to form an angle of 45 degrees with the easy alignment axis.

As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a vertical alignment type liquid crystal cell, those having a negative dielectric anisotropy for forming a nematic type liquid crystal are preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal Phenylcyclohexane-based liquid crystal or the like is used.
The polarizing plate used outside the liquid crystal cell is a polarizing plate composed of a polarizing film called an H film that absorbs iodine while stretching and aligning polyvinyl alcohol, and a cellulose acetate protective film, or a polarizing film composed of the H film itself. A board etc. can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Synthesis example 1
In a 300 mL three-necked flask equipped with a stirrer, a nitrogen introducing tube and a thermometer, 11.8 g of a compound represented by the following formula (6-5-1-1), 8.29 g of potassium carbonate, 1.00 g of potassium iodide, 4- 4.46 g of butyl-1-butene and 120 mL of 1-methyl-2-pyrrolidone were added, and the mixture was stirred at 90 ° C. for 3 hours under nitrogen. After completion of the reaction, toluene and water were added for extraction, drying with magnesium sulfate, concentration, and recrystallization with methanol to obtain 9 g of a compound represented by the following formula (6-5-1-2).

Synthesis example 2
In a 100 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 8.0 g of a compound represented by the following formula (6-5-1-2), 5.88 g of triethoxysilane and 0.2 M chloroplatinic acid hexahydrate Then, 40 μL of an isopropanol solution was added, deaerated, and then refluxed for 10 hours under nitrogen. Next, the reaction solution was passed through a short column of silica gel, concentrated, and then sufficiently dried to obtain a white, viscous liquid. Furthermore, this viscous liquid was purified with a silica column to obtain 3.5 g of a compound represented by the following formula (6-5-1).

Synthesis Examples 3 and 4
To give the compound represented by the Contact and formula in the same manner as in Scheme 4 for producing a compound represented by (6-5-1) (6-13-1).

[Weight average molecular weight]
It was calculated in terms of polystyrene by GPC.

[Pretilt angle]
T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p. In accordance with the method described in 2013 (1980), it was measured by a crystal rotation method using a He—Ne laser beam.

[Orientation of liquid crystal]
The presence / absence of an abnormal domain when the voltage was turned on / off (applied / released) to the liquid crystal display element was observed with a polarizing microscope, and the case where there was no abnormal domain was determined as “good”.

[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 90% or more was judged as “good”, and the other cases were judged as “bad”.

[Printability evaluation]
A 127 mm (D) × 127 mm (W) × 1.1 mm (H) glass substrate having an ITO film formed on the entire surface of one side is prepared, and a liquid crystal alignment film coating printer (Nissha Printing Co., Ltd.) is prepared on this glass substrate. The liquid crystal aligning agent obtained in the above experiment was filtered with a microfilter having a pore diameter of 0.2 μm using an Angstromer S-40L) and then applied to the transparent electrode surface. It dried with the hotplate close contact type preliminary dryer set to 80 degreeC, and baked for 60 minutes at 200 degreeC, and formed the liquid crystal aligning film on the glass substrate with an ITO film | membrane. The obtained alignment film was visually evaluated for unevenness, and “no good” was obtained when there was no unevenness, and “bad” when there was unevenness.

Example 1
In a 200 mL three-necked flask equipped with a cooling tube, 3.1 g (5 mmol) of the compound represented by the above formula (6-5-1), 12.7 g of tetraethoxysilane (abbreviated as TEOS, 60 mmol), 1-ethoxy-2 -37.4 g of propanol was added, heated to 60 ° C and stirred. The maleic anhydride 0.165g and 6.95g of maleic anhydride aqueous solution which were prepared for the 20 ml capacity | capacitance flask were added here, and also it heated and stirred at 60 degreeC for 4 hours. The solvent was distilled off from the resulting polymerization solution to a weight of 30.2 g to obtain a raw polymer solution. Furthermore, the orientation agent coating liquid S-1 with a solid content concentration of 4% by weight was obtained by adding butyl acetate. The weight average molecular weight measured by GPC was 2,200.

Examples 2-3
Hydrolytic condensation was carried out in the same manner as in Example 1 using the composition shown in Table 1 to synthesize an alignment agent coating solution.

Example 4
The aligning agent coating solution S-1 was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a spinner so that the film thickness became 0.1 μm, and 200 ° C. in an oven substituted with nitrogen. A thin film was formed by drying at 0 ° C. for 1 hour.
Next, the thin film surface was irradiated with polarized ultraviolet light 0.1 J / cm ² including a 313 nm emission line from a direction inclined by 40 degrees from the substrate normal line using a Hg—Xe lamp and a Grand Taylor prism. Next, for a pair of substrates subjected to ultraviolet irradiation treatment, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is screen-printed on the surface on which the liquid crystal alignment film is formed, and then to the substrate surface of the ultraviolet optical axis. The substrates were superposed and pressure-bonded so that the projection directions of these were antiparallel, and the adhesive was heat-cured at 150 ° C. for 1 hour. Next, after filling a negative type liquid crystal (MLC-6608 manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and form an angle of 45 degrees with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface. When the liquid crystal display element was produced, all showed favorable vertical alignment property. When a voltage of 5 V was applied, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage. When the cell was evaluated, the pretilt angle was 89.3 °, and the liquid crystal orientation and voltage holding ratio were both “good”. Moreover, it was "good" when the printability of the said orientation agent coating liquid S-1 was evaluated.

Examples 5-6
The alignment agent coating liquids S- 3 to S-4 were evaluated in the same manner as in Example 4 .
The results are shown in Table 2.

  From these facts, it can be seen that the polyorganosiloxane of the present invention is excellent in coating property, sensitivity, liquid crystal alignment property, and electrical properties and can be used extremely usefully for liquid crystal display elements.

Claims (7)

Following formula (1)

Here, Z is the following formula I photosensitive groups der cause crosslinking reaction or isomerization reaction by the light of a wavelength 200~400nm (6-1), (6-3) ~ (6-10) and (6-12 ) - (Ri der one structure represented by each 6-14), X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl having 1 to 20 carbon atoms A cross-linkage may be formed through -O- together with X of the group or other repeating unit,
A polyorganosiloxane having a repeating unit represented by the formula (1) and having a weight average molecular weight in the range of 1,000 to 100,000.

Here, m is an integer of 1 to 20, l is an integer of 2m + 1 or less, k is an integer of 1 to 10, and q is an integer of 2 to 10. The method for producing a polyorganosiloxane according to claim 1, wherein at least one selected from the group consisting of silane compounds represented by the following formula ( 1 ') is hydrolyzed and condensed.

Here, the definition of Z is the same as the above formula (1), R ₁ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ₁ is an alkoxyl having 1 to 20 carbon atoms. A group or a chlorine atom, and n is 2 or 3. The method for producing a polyorganosiloxane according to claim 2 , wherein the hydrolysis and condensation catalyst is an organic acid. The method for producing a polyorganosiloxane according to claim 2 or 3 , wherein the hydrolysis and condensation are performed in the presence of a silane compound represented by the following formula (7).
Si (R ₃ ) _t (OR ₄ ) _(4-t) (7)
Here, R ₃ is an alkyl group having 1 to 40 carbon atoms which may contain an alicyclic group or an aryl group having 6 to 20 carbon atoms, and R ₄ is an alkyl group having 1 to 20 carbon atoms. , T is 0, 1, 2 or 3. A liquid crystal alignment film obtained by irradiation with radiation polarized or unpolarized light to the film formed by the polyorganosiloxane according to claim 1. The liquid crystal display element which has a liquid crystal aligning film of Claim 5 . The liquid crystal display element according to claim 6, wherein a negative liquid crystal is used.