TWI453236B - Polyorganosiloxane, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Polyorganosiloxane, liquid crystal alignment film and liquid crystal display element

The present invention relates to a novel polyorganosiloxane, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a polyorganosiloxane which is useful for imparting liquid crystal alignment energy by polarized or non-polarized radiation and which is useful in formation of a liquid crystal alignment film, without being subjected to rubbing treatment; A liquid crystal alignment film and a liquid crystal display element having the liquid crystal alignment film.

In the past, a positive dielectric anisotropic nematic liquid crystal system has a substrate sandwich structure in which a transparent electrode having a liquid crystal alignment film is added, and if necessary, the long axis of the liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates. A liquid crystal display element having a liquid crystal cell such as a TN (torsional nematic) type, an STN (super twisted nematic) type, or an IP (in-plane switching) type is known (refer to Japanese Laid-Open Patent Publication No. Hei 56-91277 Kaiping 1-120528 bulletin).

In these liquid crystal cells, in order to align the liquid crystal in a certain direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of reciprocating rubbing of the surface of the organic film formed on the surface of the substrate in a certain direction with a cloth such as a crucible. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust is easily generated in the production, and static electricity is generated. Therefore, dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, the circuit of the TFT element is damaged by the generated static electricity, which is also a cause of a decrease in yield. And, for the future In the high-precision liquid crystal display element, unevenness is generated on the surface of the substrate in order to increase the density of the pixel, so that uniform rubbing treatment is a problem.

As another method for aligning liquid crystals in a liquid crystal cell, it is known to irradiate a polarizing film composed of polyethylene laurate, polyamidiamine, azobenzene derivative or the like formed on the surface of a substrate. Or a non-polarizing radiation, thereby imparting a light alignment method to the alignment energy of the liquid crystal. According to this method, it is possible to achieve uniform liquid crystal alignment, and it is possible to achieve uniform liquid crystal alignment. (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2000-144136, JP-A-2000-319510, JP-A-2000-281724, JP-A-9-297313, JP-A-2003-307736, JP-A-2004-163646, and Japanese Patent Publication No. 2002-250924).

However, in a liquid crystal cell such as a TN (torsional nematic) type or an STN (super twisted nematic) type, it is necessary for the liquid crystal alignment film to have a pretilt characteristic in which liquid crystal molecules are obliquely aligned at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle is usually imparted by inclining the incident radiation from the substrate normal to the incident direction of the substrate surface.

Further, as an operation mode of the 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 the substrate is also known. In this operation mode, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward one of the substrate faces. As for the method for this, the proposal has, for example, on the surface of the substrate. A method of providing a protrusion on the transparent electrode, a method of providing a stripe on the transparent electrode, and a method of tilting (pretilt) the liquid crystal alignment film from the normal direction of the substrate toward one direction in the substrate surface by using a rubbing alignment film.

It is also known that the above-described photoalignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. In other words, it is known that the tilting direction of the liquid crystal molecules when the voltage is applied can be uniformly controlled by using the vertical alignment film which imparts the alignment control force and the pretilt angle by the photo-alignment method (refer to Japanese Laid-Open Patent Publication No. 2003-307736, No. 2004-163646). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

As described above, the liquid crystal alignment film produced by the above-described photoalignment method is effective for various liquid crystal display elements. However, in the past, the light alignment film had to be irradiated with a large amount of radiation if it had to obtain a large pretilt angle, for example, it has been reported in a light alignment film containing an azobenzene derivative, in order to obtain a sufficient pretilt angle. Irradiation of 1 J/cm ² or more of the radiant line whose optical axis is inclined from the normal line of the substrate (refer to Japanese Laid-Open Patent Publication No. 2002-250924, JP-A-2004-83810, and J. of the SID 11/3, 2003, p. ).

The object of the present invention is to provide a polyorganooxynonane which is excellent in applicability and electrical properties, does not require rubbing treatment, and can be used to form a liquid crystal alignment film by irradiating a polarized or non-polarized radiation to a liquid crystal alignment energy. And its manufacturing method.

Other objects of the invention are provided by the above polyorganosiloxane Liquid crystal alignment film.

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

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

First, according to the present invention, the above objects and advantages of the present invention can be attained by a polysiloxane (hereinafter referred to as a polyorganosiloxane of the present invention) characterized by having a repeating unit represented by the following formula (1). And the weight average molecular weight is in the range of 1,000 to 100,000: Wherein, Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm, and X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 1~ The alkoxy group of 20, or may be crosslinked by -O- together with X in the other repeating unit represented by the formula (1).

Secondly, according to the present invention, the above objects and advantages of the present invention are more preferably achieved by the repeating unit represented by the above formula (1) being a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3) Organic oxane to achieve: Wherein, A ₁ and A ₂ may be the same or different, and are an alkyl group having a carbon number of 1 to 40 which may be substituted by a fluorine atom or a monovalent organic group of an alicyclic group, and B ₁ and B ₂ may be the same or different. And a fluorine atom or a cyano group, p is an integer of 0 to 4, and S ₁ and S ₂ are the same or different and are a divalent organic group having an alkylene group having 1 to 20 carbon atoms, and 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, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or the same as the other represented by the formula (2) or (3) X ₁ or X ₂ in the repeating unit together form a crosslink by -O-.

Thirdly, according to the present invention, the above objects and advantages of the present invention provide a process for producing a polyorganosiloxane of the present invention, which is characterized in that it is composed of a decane compound selected from the following formulas (4) and (5), respectively. At least one of the groups is hydrolyzed and condensed: The definitions of A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S ₂ and p are the same as the above formulas (2) and (3), and R ₁ and R ₂ may be the same or different and have a carbon number of 1~. An alkyl group of 20 or an aryl group having 6 to 20 carbon atoms, and Y ₁ and Y ₂ may be the same or different and are alkoxy groups or chlorine atoms having 1 to 20 carbon atoms, and n is 2 or 3.

Fourthly, according to the present invention, the above objects and advantages of the present invention are preferably achieved by a method for producing a polyorganosiloxane which is an organic acid in which the catalyst for hydrolysis and condensation is used.

Fifth, according to the present invention, the above object and advantage of the present invention are achieved by a method for producing the above hydrolysis and condensation in the presence of a decane compound represented by the following formula (7): Si(R ₃ ) _t (OR ₄ ) _(4-t) (7) wherein R ₃ is an alicyclic group-containing alkyl group having 1 to 40 carbon atoms 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.

Sixth, in accordance with the present invention, the above objects and advantages of the present invention are attained by a liquid crystal alignment film obtained by irradiating a film formed of the above polyorganosiloxane with a polarized or non-polarized radiation.

Seventh, according to the present invention, the above objects and advantages of the present invention are attained by a liquid crystal display element having the above liquid crystal alignment film.

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

Hereinafter, the present invention will be described in detail.

The polyorganooxynonane of the present invention has a weight represented by the above formula (1) The unit has a weight average molecular weight of 1,000 to 100,000.

In the formula (1), Z is a photosensitive group which generates 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 alkoxy group having 1 to 20 carbon atoms, or X in another repeating unit represented by the formula (1) Crosslinking is formed by -O- together.

Preferably, X is a hydroxy group, a methoxy group, an ethoxy group, and a group which crosslinks with -O-, together with X of other repeating units.

The repeating unit represented by the above formula (1) is preferably a repeating unit represented by the above formula (2) or a 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 are an alkyl group having a carbon number of 1 to 40 which may be substituted by a fluorine atom or a monovalent organic group of an alicyclic 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 to 4, and S ₁ and S ₂ are the same or different and are a divalent organic group having an alkylene group having 1 to 20 carbon atoms, and X ₁ and X ₂ may be the same or different and are a hydroxyl group or a carbon. An alkyl group of 1 to 20, an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or X _{1 in} another repeating unit represented by the formula (2) or (3) or X ₂ together forms a crosslink with -O-.

Specific examples of the base of the upper position of the germanium atom in the above formulas (2) and (3) can be exemplified by structures represented by the formulas (6-1) to (6-14), respectively:

In the equation, m is preferably an integer from 1 to 20, 1 is an integer below 2m+1, k is an integer from 1 to 10, q is an integer from 2 to 10, more preferably m is from 3 to 18, and 1 is 3~ 9, k is 2~6, q is 2~6, preferably m is 4~10, 1 is 3~7, k is 2~4, q is 2~4.

The polyorganosiloxane of the present invention preferably has a weight average molecular weight of 1,000 to 50,000.

The polyorganosiloxane of the present invention can be obtained by subjecting a decane compound of the above formula (4) or (5) to hydrolysis condensation.

In the 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 defined in the above formulas (2) and (3). Y ₁ and Y ₂ may, for example, be, for example, a chlorine atom and a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, an alkoxy group of a third butoxy group, or the like. . Among these, a chlorine atom, a methoxy group, and an ethoxy group are preferable. R ₁ and R ₂ may, for example, be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , n-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecyl, n-icosylalkyl, and aryl such as phenyl. Among these, a methyl group, an ethyl group, and a phenyl group are preferable.

Further, n in the formulas (4) and (5) is preferably 3.

The compound of the formula (4) can be obtained by a known method shown in the following Reaction Formulas 1 to 3, but is not limited to these methods. However, r in the reaction formulae 1-3 is k-2. The compound of the formula (5) can also be obtained in the same manner.

The reaction formula 1: the precursor of the compound of the formula (4) having an olefin and the triethoxy decane are heated and stirred in the presence of a very small amount of a platinum catalyst (hydroalkylation reaction), and the compound of the formula (4) can be obtained by purification. .

Reaction formula 2: heating and stirring a precursor of the compound of the formula (4) having a carboxylic acid and 3-glycidoxypropyltrimethoxydecane in the presence of an alkaline catalyst such as triethylamine to obtain a formula ( 4) Compounds.

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

Hydrolysis and condensation method of polyorganosiloxane

The polyorganosiloxane of the present invention can be obtained by hydrolyzing and condensing a decane compound represented by the above formula (4) or (5). At this time, it is better to use the above formula (7) Co-hydrolysis condensation in the presence of a decane compound.

In the formula (7), R ₃ is an alkyl group having 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.

The decane compound represented by the formula (7) is exemplified by, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-second oxybutane. Base decane, tetra-butoxy decane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butoxy Base decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, methyl triphenyloxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri-n-butyl Propoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-tert-butoxy decane, ethyl tri-tert-butoxy decane, phenyl triethoxy decane ; dimethyl dimethoxy decane, dimethyl diethoxy decane; trimethyl methoxy decane, trimethyl ethoxy decane, and the like. Preferred among these are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, and dimethyl Dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane, trimethyl ethoxy decane.

The decane compound of the formula (7) may be used in an amount of from 0 to 100 mols per mol of the decane compound of the formula (4) or the formula (5). It is better to use 1~100 moules, and better use 2~20 moules.

The hydrolysis and condensate can be obtained by reacting a decane compound with water, hydrolyzing, and partially condensing. In order to make an alkoxy silicon compound is hydrolyzed, partially condensed, per 1 mole of siloxane bonds Si (OR -Y -Y formula (4) of _1, the formula (5) and the formula ₂ (7) of the total of _four), more Use 1.0~1.5 moor water. If the amount of water is 1.0 mol or more, the possibility that the deuterium bond is unreacted is lowered, and the uniformity of the coating film is not lowered, and the storage stability of the liquid crystal alignment agent is reduced, so that it is good. The aqueous system is added intermittently or continuously in an organic solvent in which the decane compound of the present invention is dissolved. The reaction catalyst can be used at this time. In this case, the catalyst may be added to the organic solvent in advance, or may be dissolved or dispersed in water when water is added. The reaction temperature at this time is preferably from 0 to 100 ° C, more preferably from 15 to 80 ° C.

The above organic solvent is preferably an alcohol solvent, a ketone solvent, a guanamine solvent, an ester solvent or an aprotic solvent. These solvents may be used singly or in combination of two or more.

Among them, the alcohol solvent is, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, 2-methylbutyl Alcohol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, heptanol- 3. n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethylheptanol-4, n-nonanol, second-undecyl alcohol, trimethylhydrazine Alcohol, second-tetradecanol, second-pentadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc. Monool solvent; ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5 , heptane-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc. Alcohol solvent; 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, dipropylene glycol monopropyl A part of an ether solvent such as a polyvalent alcohol such as a group ether.

These alcohol solvents may be used alone or in combination of two or more.

Examples of the ketone solvent are, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentanone. , ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentane Ketone, acetonylacetone, acetophenone, fenchone, etc., and etidylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedion, 2, 4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6 a β-diketone agent such as tetramethyl-3,5-heptanedione or 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like.

These ketone solvents may be used alone or in combination of two or more.

The guanamine-based solvent is exemplified by, for example, formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, B. Indoleamine, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N -methylpyrrolidone, N- Mercaptomorpholine, N-methylpyridylpiperidine, N-methylpyridylpyrrolidone, N-ethinylmorpholine, N-ethinylpiperidine, N-ethinylpyrrolidone, and the like.

These guanamine solvents may be used alone or in combination of two or more.

The ester solvent is exemplified by, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, acetic acid. Isopropyl ester, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethyl acetate Butyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetoacetate, ethyl acetate Alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate Ethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol diacetate, methoxy acetate Triethylene glycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate Ester, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like.

These ester solvents may be used alone or in combination of two or more.

Examples of the aprotic solvent are, for example, acetonitrile, dimethyl hydrazine, N, N, N', N'-tetraethyl sulfonamide, trimethylamine hexamethylphosphate, N-methylmorpholine, N-methyl Pyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N-methylimidazole, N -A 4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl Tetrahydro-2(1H)-pyrimidinone and the like. The best of these are polyvalent alcohol solvents, polyvalent alcohol partial ether solvents, and ester solvents.

Further, a catalyst is preferably used in the hydrolysis and partial condensation reaction of the decane compound of the present invention. These catalysts can be exemplified by the following metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

The metal chelate compound can be exemplified by, for example, triethoxy. Single (acetylpyruvate) titanium, tri-n-propoxy. Single (acetylpyruvate) titanium, tri-isopropoxy. Single (acetylpyruvate) titanium, tri-n-butoxy. Single (acetylpyruvate) titanium, tri-second butoxy. Single (acetylpyruvate) titanium, tri-tert-butoxy. Single (acetylpyruvate) titanium, diethoxy. Bis(acetylpyruvyl) titanium, di-n-propoxy. Bis(acetylpyruvyl) titanium, di-isopropoxy. Bis(acetylpyruvyl) titanium, di-n-butoxy. Bis(acetylpyruvyl) titanium, di-second butoxy. Bis(acetylpyruvyl) titanium, di-t-butoxy. Bis(acetylpyruvate) titanium, monoethoxy. Reference (acetyl acetonate) titanium, mono-n-propoxy. Reference (acetyl acetonate) titanium, mono-isopropoxy. Reference (acetyl acetonate) titanium, mono-n-butoxy. Reference (acetyl acetonate) titanium, mono-second butoxy. Reference (acetyl acetonate) titanium, mono-tert-butoxy. Reference (acetyl acetonate) titanium, bismuth (acetyl acetonate) titanium, triethoxy. Mono (ethyl ethyl thioglycolate) titanium, tri-n-propoxy. Mono (ethyl ethyl thioglycolate) titanium, tri-isopropoxy. Mono (ethyl ethyl thioglycolate) titanium, tri-n-butoxy. Mono (ethyl ethyl thioglycolate) titanium, tri-second butoxy. Mono (ethyl ethyl thioglycolate) titanium, three - third Butoxy. Mono (ethyl ethyl thioglycolate) titanium, diethoxy. Bis(ethylacetoxyacetic acid) titanium, di-n-propoxy. Bis(ethylacetoxyacetic acid) titanium, di-isopropoxy. Bis(ethylacetoxyacetic acid) titanium, di-n-butoxy. Bis(ethylacetoxyacetic acid) titanium, di-second butoxy. Bis(ethylacetoxyacetic acid) titanium, di-t-butoxy. Bis(ethylacetoxyacetic acid) titanium, monoethoxy. Reference (ethyl ethyl thioglycolate) titanium, mono-n-propoxy. Reference (ethyl ethyl thioglycolate) titanium, mono-isopropoxy. Reference (ethyl ethyl thioglycolate) titanium, mono-n-butoxy. Reference (ethyl ethyl thioglycolate) titanium, mono-second butoxy. Reference (ethyl ethyl thioglycolate) titanium, mono-tert-butoxy. Refractory (ethyl ethinylacetate) titanium, strontium (ethyl ethionylacetate) titanium, mono (acetyl acetonate) ginseng (ethyl acetyl thioglycolate) titanium, bis (acetyl acetonate) bis (B Titanium chelating compound such as titanium, ginseng (pyruvylpyruvate) mono(ethylacetoxyacetic acid) titanium; triethoxy. Single (acetyl acetonate) zirconium, tri-n-propoxy. Single (acetyl acetonate) zirconium, tri-isopropoxy. Single (acetyl acetonate) zirconium, tri-n-butoxy. Single (acetyl acetonate) zirconium, tri-second butoxy. Single (acetyl acetonate) zirconium, tri-tert-butoxy. Single (acetyl acetonate) zirconium, diethoxy. Bis(acetylpyruvyl)zirconium, di-n-propoxy. Bis(acetylpyruvyl)zirconium, di-isopropoxy. Bis(acetylpyruvyl)zirconium, di-n-butoxy. Bis(acetylpyruvyl)zirconium, di-second butoxy. Bis(acetylpyruvyl)zirconium, di-t-butoxy. Bis(acetylpyruvyl)zirconium, monoethoxy. Reference (acetyl acetonate) zirconium, mono-n-propoxy. Reference (acetyl acetonate) zirconium, mono-isopropoxy. Reference (acetyl acetonate) zirconium, mono-n-butoxy. Ginseng (acetyl acetonate) zirconium, single-second Butoxy. Reference (acetyl acetonate) zirconium, mono-tert-butoxy. Zirconium (acetyl acetonate) zirconium, cerium (acetyl acetonate) zirconium, triethoxy. Mono (ethyl ethinyl acetic acid) zirconium, tri-n-propoxy. Mono(ethylacetoxyacetic acid) zirconium, tri-isopropoxy. Mono (ethyl ethinyl acetic acid) zirconium, tri-n-butoxy. Mono (ethyl ethinyl acetic acid) zirconium, tri-second butoxy. Mono(ethylacetoxyacetic acid) zirconium, tri-tert-butoxy. Mono (ethyl ethinyl acetic acid) zirconium, diethoxy. Bis(ethylacetoxyacetic acid) zirconium, di-n-propoxy. Bis(ethylacetoxyacetic acid) zirconium, di-isopropoxy. Bis(ethylacetoxyacetic acid) zirconium, di-n-butoxy. Bis(ethylacetoxyacetic acid) zirconium, di-second butoxy. Bis(ethylacetoxyacetic acid) zirconium, di-tert-butoxy. Bis(ethylacetoxyacetic acid) zirconium, monoethoxy. Reference (ethyl ethyl thioglycolate) zirconium, mono-n-propoxy. Reference (ethyl ethyl thioglycolate) zirconium, mono-isopropoxy. Reference (ethyl ethyl thioglycolate) zirconium, mono-n-butoxy. Reference (ethyl ethyl thioglycolate) zirconium, mono-second butoxy. Reference (ethyl ethyl thioglycolate) zirconium, mono-tert-butoxy. Zirconium (ethyl ethyl thioglycolate) zirconium, cerium (ethyl ethinyl acetic acid) zirconium, mono(ethyl thioglycolic acid) ginseng (ethyl ethyl phthalic acid) zirconium, bis (acetyl acetonate) bis (B Zirconium chelate compound such as zirconium thioglycolate, zirconium (acetyl acetonate) mono(ethylacetylacetic acid) zirconium; ginseng (acetate pyruvate) aluminum, ginseng (ethyl acetoacetate) aluminum, etc. Aluminum chelate compound.

The organic acid can be exemplified by, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, azelaic acid. Gallic acid, butyric acid, trimellitic acid, arachidonic acid, Acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloro Acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like.

The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like.

The organic base can be exemplified by, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine. , triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like.

The inorganic base can be exemplified by, for example, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide or the like.

Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and titanium sequestration compounds and organic acids are more preferred. These may be used singly or in combination of two or more.

The amount of the catalyst to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the combination of the compound (4), the compound (5) and the compound (7) (in terms of a complete hydrolysis condensation product). 0.001 to 1 part by weight.

The liquid crystal alignment agent of the present invention preferably dissolves or disperses the above hydrolysis and condensation product in an organic solvent.

As the organic solvent, organic solvents represented by the following formulas (8), (9) and (10), respectively:

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

Specific examples of the organic solvent represented by the formula (8) are exemplified by 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monoacetate. , dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether and the like. Preferred among these are propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

Specific examples of the organic solvent represented by the formula (9) are exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether (butyl cellulolytic). ), ethylene glycol monopentyl ether, Ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl card Alcohol, ethyl carbitol, propyl carbitol, butyl carbitol, and the like. Preferred among these are ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellulolytic), and ethylene glycol monopentyl ether.

Specific examples of the organic solvent represented by the formula (10) can be exemplified by n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and acetic acid second. Amyl ester, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate , amyl acetate, isoamyl acetate, and the like. Preferred among these are, for example, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and second amyl acetate.

A surfactant or the like may be added to the liquid crystal alignment agent obtained by the present invention. As the surfactant, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or the like can be exemplified. Further, examples thereof include a cerium oxide surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant, and the like.

Further, the liquid crystal alignment agent of the present invention may contain a functional decane-containing compound or an epoxy group-containing compound from the viewpoint of improving adhesion to the surface of the substrate. The functional decane-containing compound can be exemplified by, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-Amino B 3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-amine Propyltrimethoxydecane, N-triethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxy矽alkylpropyltrisethyltriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazaindene Alkane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl- 3-Aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3 -Aminopropyltriethoxydecane, N-bis(oxiranyl)-3-aminopropyltrimethoxydecane, N-bis(oxiranyl)-3-aminopropyl Triethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxy Alkane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl Ethyltriethoxydecane, and the like. Further, examples of the epoxy group-containing compound are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-di Glycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

The ratio of the polyorganooxane to the solvent in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity and volatility, but the ratio of the polyorganosiloxane (solid content concentration) in the liquid crystal alignment agent is aggregated. in terms of silicon atom of ₂ SiO SiO ₂ concentration of siloxane contained in the organic silicon, preferably 0.01 to 70% by weight, more preferably 0.05 to 60 wt%, and more preferably 1 to 30 wt%. The liquid crystal alignment agent of the present invention is preferably applied to the surface of the substrate by, for example, a roll coating method, a spin coating method, a printing method, or the like, followed by drying to form a coating film of the liquid crystal alignment film, but when solid. When the concentration of the component is less than 0.01% by weight, the film thickness of the coating film is too small, and a good liquid crystal alignment film may not be obtained. When the solid content concentration exceeds 70% by weight, it is difficult to obtain a good liquid crystal because the film thickness of the coating film is too large. The alignment film and the increase in the viscosity of the liquid crystal alignment agent may also deteriorate the coating properties.

Liquid crystal alignment film

A method of forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention is exemplified by, for example, the following method. First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the transparent conductive film is provided, for example, by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, for example, at 40 to 300 ° C. Heating at a temperature forms a coating film. At this time, the polyorganosiloxanes cause a crosslinking reaction with each other. In order to sufficiently cause cross-linking, it is preferably carried out at 150 to 250 ° C for 10 minutes to 3 hours. Heating can be carried out 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, in terms of solid content.

As the substrate, for example, glass such as float glass or soda lime glass can be used. A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate.

As the transparent conductive film, for example, a NESA film composed of SnO ₂ , an ITO film composed of In ₂ O ₃ -SnO ₂ or the like can be used. The patterning of the transparent conductive films can be performed by heat. A method of etching or pre-masking.

When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate and the transparent conductive film and the coating film, a compound containing a functional decane, a titanate or the like may be applied to the substrate and the transparent conductive film in advance.

Next, the coating film is irradiated with linearly polarized light to partially polarized radiation or non-polarized radiation, depending on the case, and further heat-treated at a temperature of 150 to 250 ° C to impart liquid crystal alignment energy. As for the radiation, ultraviolet rays and visible light having a wavelength of 200 to 400 nm can be used. When the radiation to be used is linearly polarized to partially polarized, the irradiation is performed in a direction perpendicular to the substrate surface, and the pretilt angle may be applied from the oblique direction, or may be combined. When illuminating the unpolarized radiation, the direction of illumination must be oblique.

As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light of the above preferred wavelength range can be obtained by a combination of a filter, a grating, and the like with the above-mentioned light source.

Further, the "pretilt angle" in the present invention means an angle at which liquid crystal molecules are inclined from a direction parallel to the substrate surface.

Liquid crystal display element

The liquid crystal display element formed using the liquid crystal alignment agent of the present invention is produced as follows. Preparing a substrate on which the liquid crystal alignment film is formed, and arranging the two sheets so that the polarization direction of the polarized radiation that illuminates the liquid crystal alignment film is at a predetermined angle, and sealing the peripheral portion between the substrates with a sealant to fill the liquid crystal. Sealing the filling holes constitutes a liquid crystal cell. Next, the liquid crystal cell is preferably heated to a temperature at which the liquid crystal used is an isotropic phase, and then cooled to room temperature to remove the flow alignment at the time of injection.

Therefore, the polarizing plate is bonded to the polarizing plate in the direction in which the polarizing direction of the polarizing plate is aligned with the liquid crystal alignment film of each substrate, thereby forming a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the two substrates on which the liquid crystal alignment film is formed can be arbitrarily obtained by adjusting the angle formed by the polarization direction of the irradiated linear polarized radiation and the angle between each substrate and the polarizing plate. A liquid crystal display element having a TN type or STN type liquid crystal cell. On the other hand, when the liquid crystal alignment film is vertically aligned, the two substrates on which the liquid crystal alignment film is formed are configured to be parallel to the alignment axis, and at this time, the alignment is easily 45 degrees with the alignment direction and the alignment. The polarizing plate is attached to the angle to form a liquid crystal display element having a vertical alignment type liquid crystal cell.

As the above-mentioned sealant, for example, a curing agent and an epoxy resin containing an alumina ball as a separator can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. Further, in the case of a vertical alignment type liquid crystal cell, it is preferred to form a negative dielectric anisotropy of a nematic liquid crystal, for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, or a Schiff base liquid crystal. Azoxy Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, or the like.

The polarizing plate used for the outer side of the liquid crystal cell can be exemplified by a polarizing plate called a polarizing film of an H film which absorbs iodine by sandwiching a polyvinyl alcohol while being aligned with a polyvinyl alcohol, or a polarizing plate made of an H film. Wait.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

Synthesis Example 1

Under nitrogen, a compound of the following formula (6-5-1-1), 8.29 g of potassium carbonate, 1.00 g of potassium iodide, 4.46 was added to a 300 ml three-necked reaction flask equipped with a stirrer, a nitrogen introduction tube and a thermometer. 4-butyl-1-butane and 120 ml of 1-methyl-2-pyrrolidone were stirred and stirred at 90 ° C for 3 hours. After completion of the reaction, the mixture was extracted with toluene and water, dried over magnesium sulfate, concentrated, and then recrystallized from methanol to give 9 g of the compound of formula (6-5-1-2).

Synthesis Example 2

8.0 g of the compound represented by the following formula (6-5-1-2), 5.88 g of triethoxydecane and 40 μl of 0.2 M chlorination were added to a 100 ml three-necked reaction flask equipped with a reflux tube and a nitrogen introduction tube. The platinum acid hexahydrate isopropanol solution was degassed and refluxed under nitrogen for 10 hours. Next, the reaction solution is passed through a short column of tannin, concentrated, and then sufficiently dried to obtain white. Color, viscous liquid. Further, the viscous liquid was purified by a gel column to obtain 3.5 g of the compound represented by the following formula (6-5-1).

Synthesis Example 3, 4

The compound represented by the following formula (6-2-1) and the compound represented by the following formula (6-13-1) are obtained by the same method as the reaction formula 4 of the compound represented by the above (6-5-1):

[weight average molecular weight]

Calculated by GPC converted to polystyrene.

[pretilt angle]

He-Ne laser light was used according to the method described in T.J. Scheffer et. al. J. Appl. Phys. vo. 19, p. 2013 (1980) by crystallization rotation method.

[Liquid alignment]

The liquid crystal display element was opened by a polarizing microscope. Whether there is an abnormal area when the voltage is turned off (applied or released), and it is judged as "good" when there is no abnormal area.

[voltage maintenance rate]

After applying a voltage of 5 V to the liquid crystal display element for 60 μsec and applying it at intervals of 167 msec, the voltage holding ratio after 167 msec was released was measured. The measuring device was a VHR-1 manufactured by Dongyang Technology Co., Ltd. When the voltage holding ratio was 90% or more, it was judged as "good", and otherwise it was judged as "poor".

[Printability evaluation]

A 127 mm (D) × 127 mm (W) × 1.1 mm (H) glass substrate of an ITO film is prepared on one surface of a single surface, and a liquid is used on the glass substrate. A crystal alignment coating machine (Ongustoromer S-40L, manufactured by Nippon Photo Printing Co., Ltd.) was used, and the liquid crystal alignment agent obtained in the above experiment was filtered through a microfilter having a pore size of 0.2 μm, and then applied onto a transparent electrode surface. The film was dried by a hot plate-type preliminary preheater set at 80 ° C, and fired at 200 ° C for 60 minutes to form a liquid crystal alignment film on the glass substrate to which the ITO film was attached. The spots of the obtained alignment film were visually evaluated, and those who had no spots were "good", and those who saw spots were "poor".

Example 1

Add 3.1 g (5 mmol) of the compound represented by the above formula (6-5-1) and 12.7 g of tetraethoxydecane (referred to as TEOS, 60 m) to a 200 ml three-necked reaction flask equipped with a cooling tube. Moir), 37.4 g of 1-ethoxy-2-propanol, was stirred with heating at 60 °C. At this time, an aqueous solution of 0.165 g of maleic anhydride and 6.95 g of water in anhydrous maleic anhydride, which was formulated in a reaction flask having a capacity of 20 ml, was added, and the mixture was further heated at 60 ° C for 4 hours and stirred. The solvent was distilled off from the obtained polymerization solution to obtain a raw material polymer solution having a weight of 302 g. Further, butyl acetate was added to obtain an alignment agent coating liquid S-1 having a solid concentration of 4% by weight. The weight average molecular weight measured by GPC was 2,200.

Example 2~4

Hydrolysis condensation was carried out in the same manner as in Example 1 in the composition shown in Table 1, and an alignment agent coating liquid was synthesized.

Example 5

The above-mentioned alignment agent coating liquid was coated with S-1 at a film thickness of 0.1 μm on a transparent electrode surface of a glass substrate with a transparent electrode composed of an ITO film, and was ventilated by nitrogen gas using a spin coater. The film was dried in an oven at 200 ° C for 1 hour to form a film.

Next, using a Hg-Xe lamp and Glan-Taylor Prisms, the surface of the film was irradiated from the substrate normal at a direction inclined by 40 degrees with a polarized ultraviolet ray of 313 nm ray at 0.1 J/cm ² . Next, the substrate is subjected to ultraviolet irradiation, and an epoxy resin adhesive having a diameter of 5.5 μm is applied onto the surface on which the liquid crystal alignment film is formed, so as to be incident on the substrate surface with the ultraviolet light axis. The substrate was bonded and pressed in an antiparallel manner, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608 manufactured by Merck Co., Ltd.) was filled from the liquid crystal injection port between the pair of substrates, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. Then, the polarizing plates are bonded to the outer surface of the substrate so that the polarizing directions thereof are perpendicular to each other, and the liquid crystal alignment film is bonded to the ultraviolet light axis at an angle of 45 degrees toward the substrate surface to form a liquid crystal display element. A good vertical alignment. A voltage of 5 V was applied, and the change in brightness of the liquid crystal display element corresponding to the applied voltage on-off was observed. The pretilt angle of the above unit was evaluated to be 89.3°, and the liquid crystal alignment property and the voltage maintenance ratio were all "good". Moreover, the printability of the above-mentioned alignment agent coating liquid S-1 was evaluated as "good".

Example 6-8

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

From the above data, it is shown that the polyorganosiloxane of the present invention is excellent in coatability, sensitivity, liquid crystal alignment property, and electrical characteristics, and can be extremely usefully used in liquid crystal display elements.

Effect of the invention

When the polyorganosiloxane of the present invention is used, the liquid crystal alignment film can be obtained with a smaller amount of radiation irradiation than in the case of the conventional photoalignment method. Therefore, when the liquid crystal alignment film is used for a liquid crystal display element, the liquid crystal display element can be manufactured more cheaply than ever. Thus, the liquid crystal display elements can be effectively applied to various devices such as a desktop computer, a watch, a clock, a counting display panel, a word processor, a personal computer, or a liquid crystal television.

Claims (7)

A polyorganosiloxane having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 1,000 to 100,000, and a repeating unit represented by the above formula (1) is represented by the following formula (2) Repeat unit or repeat unit represented by the following formula (3): Wherein Z is a photosensitive group which generates a crosslinking reaction or an isomerization reaction at a wavelength of 200 to 400 nm, and X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number of 1 to 20 The alkoxy group may be crosslinked with -O- together with X in the other repeating units represented by the formula (1), and A ₁ and A ₂ may be the same or different and have a carbon number of 1~. An alkyl group or a alicyclic group monovalent organic group which may be substituted by a fluorine atom, and B ₁ and B ₂ may be the same or different and are a fluorine atom or a cyano group, and p is an integer of 0 to 4, S ₁ , S ₂ may be the same or different and is a divalent organic group having an alkylene group having 1 to 20 carbon atoms, and 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, and a carbon number of 6 An aryl group of ~20, an alkoxy group having 1 to 20 carbon atoms, or may be crosslinked by -O- together with X ₁ or X ₂ in other repeating units represented by the same formula (2) or (3) . A method for producing a polyorganosiloxane according to the first aspect of the invention, characterized in that at least one selected from the group consisting of decane compounds represented by the following formulas (4) and (5) is at a reaction temperature of 0 with water. Hydrolysis and condensation after ~100 ° C reaction: The definitions of A ₁ , A ₂ , B ₁ , B ₂ , S ₁ , S ₂ and p are the same as the above formulas (2) and (3), and R ₁ and R ₂ may be the same or different and have a carbon number of 1~. An alkyl group of 20 or an aryl group having 6 to 20 carbon atoms, and Y ₁ and Y ₂ may be the same or different and are alkoxy groups or chlorine atoms having 1 to 20 carbon atoms, and n is 2 or 3. The manufacturing method of claim 2, wherein the catalyst for hydrolysis and condensation is an organic acid. The production method according to claim 2 or 3, wherein the hydrolysis and condensation are carried out in the presence of a decane compound represented by the following formula (7): Si(R ₃ ) _t (OR ₄ ) _(4-t) (7 ₎ Wherein R ₃ is an alkyl group having 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. A liquid crystal alignment film obtained by irradiating a polarized or non-polarized radiation to a film formed of the polyorganosiloxane of the first application of the patent application. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 5 of the patent application. For example, a liquid crystal display element of claim 6 is a negative type liquid crystal.