KR101442878B1 - Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

Liquid crystal aligning agent of the present invention, a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (R is a just a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), selected from the group consisting of -CH = CH ₂ and -SO ₂ Cl And a radiation-sensitive polyorganosiloxane obtained by reacting a cinnamic acid derivative having at least one group selected from the group consisting of an oxetane ring and a polyorganosiloxane having an oxetane ring.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment material, a liquid crystal alignment material, a liquid crystal alignment material,

The present invention relates to a liquid crystal aligning agent, a process for producing a liquid crystal alignment film, and a liquid crystal display device.

Conventionally, a nematic liquid crystal having a positive dielectric anisotropy is made into a sandwich structure with a transparent electrode-attached substrate having a liquid crystal alignment film, and TN ( (JP-B-56-91277 and JP-A-2005-227558) are known in which liquid crystal cells such as Twisted Nematic (TWN), Super Twisted Nematic (STN) ) 1-120528).

In such a liquid crystal cell, in order to orient the liquid crystal molecules in a predetermined direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the surface of the organic film formed on the substrate surface is rubbed in one direction with a cloth such as rayon. However, when the formation of the liquid crystal alignment film is carried out by rubbing treatment, dust and static electricity tend to be generated in the process, so that dust adheres to the surface of the alignment film, which causes a problem of display defects. Particularly, in the case of a substrate having a TFT (Thin Film Transistor) device, circuit breakage of the TFT element occurs due to the generated static electricity, which is a cause of a decrease in yield. In addition, in a liquid crystal display device which becomes more and more precise in the future, irregularities are formed on the surface of the substrate as the density of pixels becomes higher, and it becomes difficult to uniformly perform the rubbing treatment.

As another means for orienting the liquid crystal in the liquid crystal cell, a method of irradiating polarized or unpolarized radiation to a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the surface of the substrate, The orientation method is known. According to this method, it is possible to realize uniform liquid crystal alignment without generating static electricity or dust (Japanese Patent Laid-Open Nos. 6-287453, 10-251646, 11-2815, 11-152475, 2000-144136, 2000-319510, 2000-281724, and Japanese Patent Application Laid- Japanese Patent Application Laid-Open Nos. 9-297313, 2003-307736, 2004-163646, and 2002-250924).

However, in a liquid crystal cell such as a TN (twisted nematic) type or STN (super twisted nematic) type liquid crystal alignment film, it is necessary to have a pretilt angle characteristic in which liquid crystal molecules are tilted at a predetermined angle with respect to the substrate surface. In the case of forming a liquid crystal alignment film by the photo alignment method, the pretilt angle is given by inclining the incidence direction of the radiation to be irradiated onto the substrate surface from the normal of the substrate.

On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having a negative dielectric anisotropy are vertically oriented on a substrate is also known as an operation mode of the liquid crystal display element different from the above. 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 that the liquid crystal molecules are inclined in one direction in the substrate surface from the substrate normal direction. As a means for this, for example, a method of providing protrusions on the surface of a substrate, a method of providing a stripe on a transparent electrode, and a method of using a rubbing alignment film to slightly tilt the liquid crystal molecules toward one direction in the substrate surface Pretilt) method and the like have been proposed.

It is known that the photo alignment method is also useful as a method of controlling the oblique direction of the liquid crystal molecules in the liquid crystal cell of the vertical alignment mode. That is, it has been 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 having the alignment control ability and the pretilt angular expression property by the photo alignment method (Japanese Patent Application Laid- Japanese Patent Laid-Open Nos. 307736, 2004-163646, 2004-83810, 9-211468, and 2003-114437).

Thus, the liquid crystal alignment film produced by the photo alignment method can be effectively applied to various liquid crystal display elements. However, the conventional photo alignment film has a problem in that the irradiation dose required for obtaining a large pretilt angle is large. For example, when a liquid crystal aligning ability is imparted to a thin film containing an azobenzene derivative by a photo alignment method, in order to obtain a sufficient pretilt angle, the optical axis of the thin film containing azobenzene derivative should be irradiated with the radiation inclined from the substrate normal by 10,000 J / m ² or more (See Japanese Patent Application Laid-Open Nos. 2002-250924 and 2004-83810 and J. of the SID 11/3, 2003, p579).

An object of the present invention is to provide a liquid crystal aligning agent which provides a liquid crystal alignment film having good liquid crystal aligning ability even at a low exposure dose by irradiating with polarized light or non-polarized light without rubbing treatment, a process for producing the liquid crystal alignment film, Which is excellent in various performances of the liquid crystal display device.

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

According to the present invention, said object of the present invention is firstly,

Having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ and -SO ₂ Cl Namsan derivatives,

A polyorganosiloxane having an oxetane ring

To obtain a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane.

The above object of the present invention is secondly,

And a method of forming a liquid crystal alignment film for applying a liquid crystal aligning agent on a substrate to form a coating film and irradiating the coating film with radiation.

The above object of the present invention is, thirdly,

And a liquid crystal alignment film formed from the above liquid crystal aligning agent.

Liquid crystal aligning agent of the present invention, a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (R is a just a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), selected from the group consisting of -CH = CH ₂ and -SO ₂ Cl A cinnamic acid derivative having at least one group selected from the group consisting of

A polyorganosiloxane having an oxetane ring (hereinafter referred to as " polyorganosiloxane having an oxetane ring)

To obtain a radiation-sensitive polyorganosiloxane.

[Derivatives of cinnamic acid]

A carboxyl group, a hydroxyl group used in the present invention, -SH, -NCO, -NHR (R is a just a hydrogen atom or an alkyl group having 1 to 6), -CH = CH ₂ and -SO ₂ 1 is selected from the group consisting of Cl It is preferable that the cinnamic acid derivative having at least two groups is a compound represented by the following formula (A-1) or a compound represented by the following formula (A-2).

≪ Formula (A-1) >

(In the formula (A-1), R ¹ is a monovalent organic group having 3 to 40 carbon atoms including an alkyl group having 1 to 40 carbon atoms or an alicyclic group, provided that a part or all of the hydrogen atoms of the alkyl group are substituted with a fluorine atom R ² is a single bond, an oxygen atom, -COO- or -OCO-, R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group, R ⁴ represents a single bond, an oxygen atom, -COO- or -OCO-, and R ⁵ represents a single bond, a methylene group, a C 2 - 10 is an alkylene group or a divalent aromatic group, R ⁵ is a single bond when R ⁶ is R ⁶ is a carboxyl group, a hydroxyl group, -SH, a hydrogen atom, R ⁵ is a methylene group, an alkylene group or a divalent aromatic group, when - an NCO, -NHR, -CH = CH ₂ or -SO ₂ Cl, wherein R is again just a hydrogen atom An alkyl group having 1 to 6, R ⁷ is a fluorine atom, a methyl group or a cyano group, a is an integer from 0 to 3, b is an integer of from 0 to 4)

≪ General Formula (A-2) >

(In the formula (A-2), R ⁸ is a monovalent organic group having 3 to 40 carbon atoms, which is an alkyl group having 1 to 40 carbon atoms or an alicyclic group or an aromatic group, provided that a part or all of the hydrogen atoms of the alkyl group is a fluorine atom may be substituted, R ⁹ is a single bond, an oxygen atom, -COO- or -OCO-, R ¹⁰ is a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent aromatic group, a divalent alicyclic group, a divalent R ¹¹ is a single bond, -OCO- (CH ₂ ) _e -, - (CH ₂ ) _e -, or a bivalent fused ring group, (CH ₂ ) _g - or -O- (CH ₂ ) _i -, e, g and i are each an integer of 1 to 10, R ¹² is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR , and -CH = CH ₂ or -SO ₂ Cl, but wherein R is a hydrogen atom or an alkyl group having 1 to 6, R ¹³ is a fluorine atom, a methyl group or A cyano group, c is an integer from 0 to 3, d is an integer of from 0 to 4)

Examples of the alkyl group having 1 to 40 carbon atoms for R ^{1 in} the above formula (A-1) include an alkyl group having 1 to 20 carbon atoms, provided that some or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom . Examples of such alkyl groups include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4 , A 5,5,5-heptafluoropentyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2- (perfluorobutyl) 2- (perfluorooctyl) ethyl group, 2- (perfluorodecyl) ethyl group, and the like. Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ¹ include a cholesteryl group, a cholestanyl group and an adamantyl group.

Examples of the divalent aromatic group represented by R ³ include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, Tetrafluoro-1,4-phenylene group and the like; Examples of the divalent alicyclic group represented by R ³ include 1,4-cyclohexylene group and the like; Examples of the divalent heterocyclic group of R ³ include a 1,4-pyridylene group, a 2,5-pyridylene group and a 1,4-furanylene group; Examples of the divalent condensed ring group of R ³ include a naphthylene group and the like.

The bivalent aromatic group represented by R ⁵ includes, for example, a 1,4-phenylene group.

Examples of the compound represented by the above formula (A-1) include a compound represented by each of the following formulas (A-1-C1) to (A-1-C24) as the cinnamic acid derivative having a carboxyl group ;

(Wherein R ¹ has the same meaning as in the above formula (A-1), and f is an integer of 1 to 10)

Examples of the cinnamic acid derivative having a hydroxyl group include compounds represented by the following formulas (A-1-O1) to (A-1-O13), respectively.

(Wherein R ¹ has the same meaning as in the above formula (A-1), and f is an integer of 1 to 10)

Examples of the alkyl group having 1 to 40 carbon atoms represented by R ⁸ in the formula (A-2) include an alkyl group having 1 to 20 carbon atoms, provided that a part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom desirable. Examples of such an alkyl group include those exemplified as the alkyl group of R ^{1 in} the above formula (A-1). Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ⁸ include a cholesteryl group, a cholestanyl group and an adamantyl group. As the monovalent organic group having 3 to 40 carbon atoms and containing an aromatic group of R ⁸ , for example,

(Wherein R ^I represents an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms) Lt; RTI ID = 0.0 > fluoroalkyl < / RTI >

And a group represented by any one of them.

Examples of the bivalent aromatic group, bivalent alicyclic group, bivalent heterocyclic group or divalent fused ring group of R ¹⁰ include a divalent aromatic group of R ^{3 in} the above formula (A-1), a divalent alicyclic group , A divalent heterocyclic group or a divalent condensed ring group, respectively.

Examples of the compound represented by the above formula (A-2) include a compound represented by each of the following formulas (A-2-C1) to (A-2-C6) as a cinnamic acid derivative having a carboxyl group ;

(Wherein R ⁸ has the same meaning as in the above formula (A-2), and a is an integer of 1 to 10)

Examples of the cinnamic acid derivative having a hydroxyl group include compounds represented by the following formulas (A-2-O1) to (A-2-O5), respectively.

(Wherein R ⁸ has the same meaning as in the above formula (A-2), and h is an integer of 1 to 10)

The compound represented by the above formula (A-1) or (A-2) can be synthesized by a conventional method of organic chemistry.

For example, the compound represented by the above formula (A-1-C1) can be prepared by, for example, heating and reacting hydroxycinnamic acid with a halogenated alkyl having an alkyl group corresponding to R ¹ in the presence of a suitable base such as potassium carbonate , Or an appropriate alkali aqueous solution such as sodium hydroxide.

The compound represented by the above formula (A-1-C2) can be obtained by, for example, hydroxycinnamic acid and an alkylcarboxylic acid chloride having an alkyl group corresponding to R ¹ in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C to room temperature Lt; / RTI >

The compound represented by the above formula (A-1-C4) can be obtained by, for example, reacting methyl hydroxybenzoate with an alkyl halide or an alkyl halide having an alkyl group corresponding to R ¹ in the presence of a suitable base such as potassium carbonate, , Followed by hydrolysis with an appropriate alkaline aqueous solution such as sodium hydroxide or the like, followed by conversion to the acid chloride with thionyl chloride. This is then reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at 0 < At room temperature.

The compound represented by the above formula (A-1-C5) can be produced, for example, by reacting an alkylcarboxylic acid chloride having an alkyl group corresponding to R ¹ with hydroxybenzoic acid in the presence of a suitable base such as triethylamine at a temperature of 0 ° C to room temperature , Followed by reaction with hydroxycinnamic acid at a temperature of 0 ° C to room temperature in the presence of a suitable base such as potassium carbonate or the like.

The compound represented by the above formula (A-1-C6) can be prepared by, for example, using 4-alkylbenzoic acid as an acid chloride with thionyl chloride, and reacting it with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at 0 [ At room temperature.

The compound represented by the above formula (A-1-C7) can be obtained by, for example, reacting methyl 4-hydroxycyclohexylcarboxylate with a halogenated alkyl having an alkyl group corresponding to R ¹ in the presence of a suitable alkali such as sodium hydride or metal sodium , Followed by hydrolysis with an alkaline aqueous solution such as sodium hydroxide to give the thionyl chloride chloride. The resulting product is reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C to room temperature Lt; / RTI >

The compound represented by the above formula (A-1-C8) can be produced by, for example, reacting a 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R ¹ with thionyl chloride using an acid chloride in the presence of a suitable base such as potassium carbonate At a temperature of from 0 째 C to room temperature.

The compound represented by the above general formula (A-1-C9) can be obtained by reacting 4-acetylbenzoic acid with sodium hydroxide in the presence of an alkyl halide corresponding to R ¹ and hydroxybenzaldehyde in the presence of a base such as potassium carbonate, Lt; RTI ID = 0.0 > aldol < / RTI > Compounds represented by each of the above formulas (A-1-C10) to (A-1-C15) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-2-C1) can be produced by, for example, reacting 4-iodophenol and an alkyl acrylate having an alkyl group corresponding to R ¹ with palladium and amine as a catalyst (generally referred to as " ) Reaction), and then ring-opening a desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride to the reaction product.

The compound represented by the above formula (A-2-C2) can be obtained by aldol condensation of 4-alkyl acetophenone corresponding to R ¹ and 4-formylbenzoic acid in the presence of sodium hydroxide. The compound represented by the above formula (A-2-C3) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-2-C4) can be obtained by aldol condensation of 4-alkyl acetophenone corresponding to R ¹ and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A-2-C5) can also be obtained by a method analogous thereto.

The compound represented by the above formula (A-1-O1) is obtained by reacting a halogenated alkyl having an alkyl group corresponding to R ¹ with 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond, - allyl condensation of hydroxyacetophenone in the presence of sodium hydroxide. The compounds represented by the above formulas (A-1-O2) to (A-1-O7) can also be obtained by the above-described method.

The compound represented by the above formula (A-2-O1) can be produced by, for example, reacting 4-iodophenol and an alkyl acrylate having an alkyl group corresponding to R ¹ with palladium and amine as catalysts Quot;).

The compound represented by the above formula (A-2-O2) can be obtained by aldol condensation of 4-alkyl acetophenone corresponding to R ¹ and 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A-2-O3) can also be obtained by the above-mentioned method.

[Polyorganosiloxane having an oxetane ring]

The above polyorganosiloxane having an oxetane ring is preferably at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof and a condensate of a hydrolyzate Do.

≪ Formula (S-1) >

(In the formula (S-1), X is a monovalent organic group having a structure represented by the following formula (X-1), Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms

≪ Formula (X-1) >

(In the formula (X-1), R ¹⁴ is an alkyl group having 1 to 6 carbon atoms, and "*"

The alkyl group of the group R ¹⁴ in the group X in the formula (S-1) is preferably a methyl group, ethyl group, n-propyl group or n-butyl group.

The group X in the formula (S-1) is preferably a group represented by the following formula (X-2) and is preferably a group represented by the following formula (X-3).

≪ Formula (X-2) >

One (Formula (X-2), R ¹⁴ has the same meaning and, R ¹⁵ is methylene group or during the 2 to 6 carbon atoms which may be interrupted by an oxygen atom alkylene group as those in the general formula (X-1) &Quot; and " * " indicates a combined hand)

≪ General Formula (X-3) >

Examples of the alkoxyl group having 1 to 20 carbon atoms for Y ¹ include a methoxyl group, ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, s-butoxyl group, Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n-decyl group, and the like.

The polyorganosiloxane having an oxetane ring preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 100,000, more preferably 1,000 to 10,000, and more preferably 1,000 to 6,000 desirable.

The polyorganosiloxane having such an oxetane ring is preferably a silane compound having an oxetane ring, or a mixture of a silane compound having an oxetane ring and another silane compound, preferably in the presence of an appropriate organic solvent, water and a catalyst, Can be synthesized by decomposition or hydrolysis / condensation.

Examples of the silane compound having an oxetane ring include compounds represented by the following formula (3-1).

≪ Formula (3-1) >

(In the formula (3-1), R ¹⁶ is a methyl group or an ethyl group)

Examples of the other silane compounds include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxy 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3- Epoxycyclohexyl) ethyltriethoxysilane, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxy Silane, tetra-sec-butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluoro N-propoxysilane, fluoro-n-propoxysilane, fluoro-n-butoxysilane, fluoro-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichloro Silane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri- Butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltri- (Perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (Perfluoro-n-hexyl) ethyl (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- (Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- Octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro- Butoxy silane, 2- (perfluoro-n-octyl) ethyl tri-n-butoxy silane, 2- (perfluoro- Hydroxymethyltriethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri- Butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- ( (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltriethoxysilane, 3- Propyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n -Butoxysilane, 3-mercaptopropyltris-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichloro N-butoxysilane, allyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri- Phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec- Butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxy silane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, Propyloxy silane, dimethyl di-n-butoxy silane, dimethyl di-sec-butoxy silane, dimethyl di-n-butoxy silane, dimethyldimethoxy silane, dimethyl diethoxy silane, dimethyl di- (Perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, ( (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, Propoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di- (Methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (Methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-n-propoxysilane, (Vinyl) di-sec-butoxysilane, divinyl di N-propoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, -Butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxy Silane, diphenyl di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n Propoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) (Methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, ((meth) Ethoxy) (methyl) di outer silane compound having one silicon atom such as phenyl silane,

X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, K- X-22-170BX, X-22-170D, X-22-170DX, X-22-170B, X-21-5846, X- X-22-176D, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- KR-200, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR- KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.); Glass resin (manufactured by Showa Denko K.K.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (manufactured by Nippon Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931 and XMS-5025 (manufactured by Chisso Corporation); Methyl silicate MS51, methyl silicate MS56 (manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (trade name, manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, and CR950 (manufactured by Showa Denko K.K.).

Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like are preferable.

The weight of the polyorganosiloxane corresponding to 1 mole of the oxetane ring is preferably 100 to 2,000 g / mol, more preferably 200 to 1,000 g / mol, in the polyorganosiloxane having an oxetane ring preferably used in the present invention desirable. Therefore, in the synthesis of the polyorganosiloxane having an oxetane ring, it is preferable to adjust and set the oxytetramine concentration of the polyorganosiloxane to obtain the ratio of the silane compound having the oxetane ring and the other silane compound to the above range Do.

Examples of the organic solvent which can be used for synthesizing the polyorganosiloxane having an oxetane ring include alcohols such as methanol, ethanol and isopropanol; Ketones such as acetone, 2-butanone and methyl isobutyl ketone, and tetrahydrofuran, toluene, 1,4-dioxane, hexane and ligroin. The amount of the organic solvent to be used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound.

The amount of water used when synthesizing the polyorganosiloxane having an oxetane ring is preferably 0.1 to 1,000 moles, more preferably 1.0 to 100 moles per 1 mole of the total silane compound.

As the catalyst to be used in synthesizing the polyorganosiloxane having an oxetane ring, a basic compound is preferable, and examples thereof include ammonia, a quaternary ammonium salt, an organic amine and the like. As the organic amine, a tertiary amine is preferable. As the catalyst, a quaternary ammonium salt or a tertiary amine is particularly preferable, and specific examples thereof include triethylamine, tripropylamine, diazabicyclo-undecene, tetramethylammonium hydroxide and the like . The amount of the catalyst to be used is preferably 1 to 100 parts by weight based on 100 parts by weight of the total silane compound.

As the reaction conditions for the synthesis of the polyorganosiloxane having an oxetane ring, suitable conditions may be employed. At least 90 mol% of the total number of hydrolyzable groups (total number of hydroxyl groups, halogen atoms and alkoxyl groups) in the total silane compounds Is preferably condensed, and it is preferable that 95 mol% or more is condensed. In order to obtain such a polyorganosiloxane, the reaction conditions are preferably a reaction at a reaction temperature of 10 to 120 DEG C, more preferably 20 to 80 DEG C, preferably 0.1 to 30 hours, more preferably 1 to 10 hours Time can be done.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. In this cleaning, it is preferable that the cleaning is performed by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt% or the like. The washing is carried out until the water layer after washing becomes neutral. Thereafter, the organic solvent layer is dried with an appropriate drying agent such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed. Thus, a polyorganosiloxane Siloxane can be obtained.

In the present invention, those commercially available as a polyorganosiloxane having an oxetane ring can also be used. As such a commercial product, for example, trade name "OX-SQ" of Toagosei Co., Ltd. and the like can be mentioned.

[Radiation-sensitive polyorganosiloxane]

The radiation-sensitive polyorganosiloxane used in the present invention can be synthesized by reacting a cinnamic acid derivative as described above with a polyorganosiloxane having an oxetane ring, preferably in the presence of a catalyst. The cinnamic acid derivative is used in an amount of preferably 0.001 to 3 mol, more preferably 0.1 to 1 mol, and still more preferably 0.2 to 0.9 mol, based on 1 mol of the oxetanyl group of the polyorganosiloxane.

In the present invention, a part of the cinnamic acid derivative may be substituted with a compound represented by the following general formula (5) so long as the effect of the present invention is not impaired. In this case, the synthesis of the radiation-sensitive polyorganosiloxane is carried out by reacting a polyorganosiloxane having an oxetane ring with a cinnamic acid derivative and a mixture of the compound represented by the formula (5).

(In the general formula (5), R < ¹⁸ > is a monovalent organic group having 3 to 40 carbon atoms, which is an alkyl group or an alkoxyl group or an alicyclic group having 4 to 20 carbon atoms, provided that a part or all of the hydrogen atoms of the alkyl group or the alkoxyl group is a fluorine atom may be substituted, R ¹⁹ is a single bond or a phenylene group, R ¹⁹ is just a phenylene group when R ¹⁸ is an alkoxyl group, R ²⁰ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (however, R Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH _2, and -SO ₂ Cl.

R ¹⁸ in Formula 5 is preferably an alkyl or alkoxyl group having 8 to 20 carbon atoms or a fluoroalkyl group or fluoroalkoxyl group having 4 to 21 carbon atoms, and R ¹⁹ is preferably a single bond or a 1,4-phenylene group And R < ²⁰ > is preferably a carboxyl group.

Preferred examples of the compound represented by the formula (5) include compounds represented by any one of the following formulas (5-1) to (5-4) ) To (5-3-3).

(Wherein h is an integer of 1 to 3, i is an integer of 3 to 18, j is an integer of 5 to 20, k is an integer of 1 to 3, m is an integer of 0 to 18, n is an integer of 1 to 18)

The compound represented by the formula (5) is a compound which reacts with the cinnamic acid derivative together with a polyorganosiloxane having an oxetanyl group to become a site giving pretilt angularity to the resulting liquid crystal alignment film. In the present specification, the compound represented by Formula 5 is hereinafter referred to as "another pretilt angle-expressing compound".

In the present invention, when different pretilt angle-expressing compounds are used together with the cinnamic acid derivative, the total use ratio of the cinnamic acid derivative and other pretilt angle-expressing compounds is the oxetanyl group 1 of the polyorganosiloxane Is preferably from 0.001 to 1.5 moles, more preferably from 0.01 to 1 mole, and still more preferably from 0.05 to 0.5 mole, based on the moles. In this case, the other pretilt angle-expressing compound is used in an amount of preferably 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the compound with the cinnamic acid derivative. When the proportion of the other pretilt angle-expressing compound is more than 50 mol%, there arises a problem that an abnormal domain occurs when the liquid crystal display element is turned ON.

Examples of the catalyst include aluminum oxide, tetrabutoxy titanium, tetraisopropoxy titanium, zinc octylate, tin octylate, aluminum acetylacetone complex, titanium acetylacetone complex, zirconium acetylacetone complex, benzyldimethylamine, paratoluene Sulfonic acid, tetraphenylphosphine bromide and the like can be used. The amount of the catalyst to be used is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polyorganosiloxane having an oxetane ring.

The reaction temperature is preferably 0 to 300 캜, more preferably 10 to 250 캜, and the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

In the synthesis of the radiation-sensitive polyorganosiloxane, organic solvents such as hydrocarbons, ethers, esters, ketones, amides and alcohols may be used as needed. The ether, ester or ketone is preferable from the viewpoints of solubility of raw materials and products, ease of purification and the like. Specific examples of particularly preferable organic solvents include toluene, xylene, diethylbenzene, mesitylene, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and cyclohexanone. The organic solvent is used in an amount such that the solid concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight.

[Other Ingredients]

The liquid crystal aligning agent of the present invention contains the above-described radiation-sensitive polyorganosiloxane.

The liquid crystal aligning agent of the present invention may further contain other components in addition to the above-mentioned radiation-sensitive polyorganosiloxane, so long as the effect of the present invention is not impaired. Examples of such other components include polymers other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as " another polymer "), heat-sensitive crosslinking agents, functional silane compounds, and surfactants.

The other polymer can be used to further improve the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the obtained liquid crystal alignment film. Such other polymers include, for example, at least one polymer selected from the group consisting of polyamic acid and polyimide; (Hereinafter also referred to as " other polyorganosiloxanes ") selected from the group consisting of polyorganosiloxanes having repeating units represented by the following formula (S-2), condensates of hydrolyzates thereof and hydrolyzates thereof, ; Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be given as examples of the poly (meth) acrylate ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative.

≪ Formula (S-2) >

(Wherein R ¹⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, Y ² is a hydroxyl group, a halogen atom, an alkoxyl group having 1 to 20 carbon atoms, 1 to 6 alkyl group)

- polyamic acid -

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound.

Examples of the tetracarboxylic acid dianhydride that can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 5,6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro- - (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b-hexahydro (Tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [ Cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride, A carboxylic acid dianhydride, a compound represented by the following formula (T-1) to And tetracarboxylic acid dianhydride represented by each of the following formulas (T-14): aliphatic or alicyclic tetracarboxylic acid dianhydride;

Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- Naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy ), Diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane 2 Anhydride, 3,3 ', 4,4'-perfluoroisopropylidene tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) (Triphenylphthalic acid) dianhydride, m-phenylene bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) dianhydride, Bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride represented by each of the following formulas (T-15) to (T-18) And aromatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydride.

Among these, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl- -c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid 2 Anhydrides and tetracarboxylic acid dianhydrides represented by the above formulas (T-1), (T-2) and (T-15) to (T-18).

These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

Examples of the diamine compounds usable for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, Diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) , 3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 2,2- Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis Bis (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis Aminophenoxy) benzene, 1,3-bis (3-amino Benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- Methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'- Dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- (p-phenyleneisopropylidene) bisaniline, 4,4 '- (m (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2- Bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 6- (4-chalconyloxy) (2,4-diaminobenzene), 6- (4'-fluoro-4-chalconyloxy) hexyloxy (2,4-diaminobenzene) (2,4-diaminobenzene), 8- (4'fluoro-4-chalconyloxy) octyloxy (2,4-diaminobenzene) 2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy- Diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestearyloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diamino Benzene, dodecyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), pentadecyloxy (3,5-diaminobenzoyl), hexadecyloxy Diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), (5-diaminobenzoyl) (2,4-diaminophenoxy) -4-trifluoromethylbenzoate represented by the following formula (D), (2,4-diaminophenoxy) -1) to (D-5);

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5)

Aromatic diamines having a hetero atom such as diaminotetraphenylthiophene; But are not limited to, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, Hexahydro-4,7-methanedanediyldimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine Aliphatic or alicyclic diamines such as tetramethylene diamine;

And diaminoorganosiloxanes such as diaminohexamethyldisiloxane and the like.

Among them, preferable examples include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'- 4,4'- (p-phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- Hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestearyloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy Diaminobenzoyl), cholestanyloxy (3,5-diamino benzoyl), cholestanoloxy (3,5-diaminobenzoyl) Diamino benzoyl) and diamine compounds represented by the above formulas (D-1) to (D-5).

These diamine compounds may be used alone or in combination of two or more.

The ratio of the tetracarboxylic acid dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid is preferably from 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride with respect to one equivalent of the amino group contained in the diamine compound , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of preferably -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably 2 to 10 Time is done. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Nonpolar polar solvents such as N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethyl urea and hexamethylphosphotriamide; m-cresol, xylenol, phenol, halogenated phenol and the like. The amount of the organic solvent (a: the total amount of the organic solvent and the below-mentioned poor solvent used together) means that the total amount of the tetracarboxylic acid dianhydride and the diamine compound (b) is preferably from 0.1 to 50% by weight, more preferably from 5 to 30% by weight, based on the weight of (a + b).

The organic solvent may be used in combination with alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. generally known as poor solvents of polyamic acid, within a range that does not cause the production of the produced polyamic acid. Specific examples of such a poor solvent include alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Ethyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl N-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane , Heptane, octane, benzene, toluene, xylene, and the like.

When the poor solvent as described above is used in the organic solvent in the production of the polyamic acid, the use ratio thereof can be appropriately set within a range in which the produced polyamic acid is not precipitated, preferably 50% by weight or less in the total solvent .

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of a liquid crystal aligning agent, or after the isolated polyamic acid is purified, For example. The isolation of the polyamic acid can be carried out by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate, drying the precipitate under reduced pressure, or a method of distilling off the reaction solution under reduced pressure using an evaporator. Alternatively, the polyamic acid can be purified by a method of dissolving the polyamic acid in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using an evaporator once or several times.

- polyimide-

The polyimide can be produced by dehydrating and ring closure of the amic acid structure of the polyamic acid obtained as described above. At this time, the entire amic acid structure may be completely imidized by dehydrating and ring closure, or only a part of the amic acid structure may be dehydrated and ring-closed to form a partial imide having an amic acid structure and an imide structure.

The dehydration ring-closure of polyamic acid can be carried out by a method of (i) heating polyamic acid, or (ii) dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydrating ring- Is done.

The reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 占 폚, more preferably 60 to 170 占 폚. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting imidized polymer may be lowered. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closing catalyst in the solution of the polyamic acid of the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the polyamic acid structural unit. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited to this. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature for the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide obtained in the above method (i) may be directly supplied to the production of a liquid crystal aligning agent, or may be provided in the production of a liquid crystal aligning agent after purification of the obtained polyimide. On the other hand, in the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent, or may be provided in the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, , Or may be provided for the production of a liquid crystal aligning agent after purification of the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by carrying out the same operation as described above as a method for isolation and purification of polyamic acid.

- other polyorganosiloxane-

At least one (other polyorganosiloxane) selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above-described formula (S-2), a hydrolyzate thereof and a condensate of a hydrolyzate, It is preferable that the weight average molecular weight in terms of polystyrene is 100 to 10,000. These other polyorganosiloxanes are preferably prepared by reacting at least one silane compound (hereinafter also referred to as " raw silane compound ") selected from the group consisting of an alkoxysilane compound and a halogenated silane compound, preferably in an appropriate organic solvent, Can be synthesized by hydrolysis or hydrolysis / condensation in the presence of a catalyst.

Examples of the raw material silane compounds usable herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- Ethoxy silane, tetra-tert-butoxy silane, tetrachlorosilane; Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- propyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopropoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-tert-butoxy silane, ethyl trichlorosilane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl trichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane Or trimethylethoxysilane is preferable.

Examples of the organic solvent that can optionally be used in the synthesis of other polyorganosiloxane include an alcohol compound, a ketone compound, an amide compound and an ester compound and other aprotic compounds. These may be used alone or in combination of two or more.

Examples of the alcohol compound include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, sec-pentanol, sec-heptanol, heptanol-3, n-octane, sec-hexanol, Octyl alcohol, sec-tetradecyl alcohol, sec-tetradecyl alcohol, sec-octadecyl alcohol, sec-octadecyl alcohol, Monoalcohol compounds such as heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monoethyl 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 mono Methyl ethyl 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 And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether. These alcohol compounds may be used singly or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, Of monoketone compounds;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, Dione compounds such as dione, 5-methyl-2,4-hexanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione. These ketone compounds may be used alone or in combination of two or more.

Examples of the amide compound include N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N- N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, and the like. These amide compounds may be used singly or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, Monoethyl ether, diethylene glycol mono-n-butyl ether acetate, 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, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, Butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like can be used. . These ester compounds may be used singly or in combination of two or more.

Examples of the other aprotic compound include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4- Pyridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro- And the like.

Of these solvents, polyhydric alcohol compounds and partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.

The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the total amount of the alkoxyl group and the halogen atom contained in the raw material silane compound , And more preferably 1 to 1.5 moles.

Examples of the catalyst that can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri- i-propoxy mono (acetylacetonate) (Acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, , Di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy Tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate ) Titanium, mono-t-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, (Acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri- (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethyl acetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, Di-sec-butoxy bis (ethylacetoacetate) titanium, di-t-butoxy (Ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis ;

Tri-n-butoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri- (Acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di-tert-butoxy mono (acetylacetonate) zirconium, n-butoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di- (Acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris Mono-i-propoxy tris (Acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium (Ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) (Ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy Bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis Acetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris Ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis Zirconium chelate compounds such as bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;

Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethyl acetoacetate) aluminum, and the like.

Examples of the organic acid 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, But are not limited to, butyric acid, butyric acid, melitoic acid, arachidonic 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, , Trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

Examples of the inorganic acid 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, diazabicyclooctane, diazabicyclononane, diazabicyclo-undecene, tetramethylammonium hydroxide, and the like.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

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

Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferable, and titanium chelate compounds or organic acids are more preferable.

The amount of the catalyst to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the raw material silane compound.

Water added in the synthesis of other polyorganosiloxanes can be added intermittently or continuously in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent.

The catalyst may be added in advance in a silane compound as a raw material or in a solution in which a silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

The reaction temperature in the synthesis of the other polyorganosiloxane is preferably 0 to 100 占 폚, more preferably 15 to 80 占 폚. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

When the liquid crystal aligning agent of the present invention contains another polymer together with the above-mentioned radiation-sensitive polyorganosiloxane, the content of the other polymer is preferably 10,000 parts by weight or less based on 100 parts by weight of the radiation-sensitive polyorganosiloxane . The more preferable content of the other polymer differs depending on the kind of the other polymer.

In the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane, a polyamic acid and a polyimide, a more preferable use ratio of the two is a radiation- The total amount of polyamic acid and polyimide relative to 100 parts by weight of the organosiloxane is 100 to 5,000 parts by weight, more preferably 200 to 2,000 parts by weight.

On the other hand, in the case where the liquid crystal aligning agent of the present invention contains the radiation-sensitive polyorganosiloxane and other polyorganosiloxane, the more preferable ratio of the two is 100 parts by weight of the radiation-sensitive polyorganosiloxane The amount of the polyorganosiloxane is 100 to 2,000 parts by weight.

When the liquid crystal aligning agent of the present invention contains another polymer together with the radiation-sensitive polyorganosiloxane, the other polymer may be at least one polymer selected from the group consisting of polyamic acid and polyimide, Siloxane.

The thermosensitive cross-linking agent can be used for stabilizing the pre-tilt angle and for improving the film strength. As the thermosensitive cross-linking agent, for example, polyfunctional epoxy compounds are effective, and examples thereof include bisphenol A type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, A cyclodiamine epoxy resin, a heterocyclic epoxy resin, an acrylic resin having an epoxy group, and the like. Examples of commercially available products thereof include Epolite 400E and 3002 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicote 828, Copper 152 and Epoxy novolac 180S (manufactured by Japan Epoxy Resin Co., Ltd.) have. When a polyfunctional epoxy compound is used as the heat-sensitive crosslinking agent, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of effectively causing a crosslinking reaction.

When the liquid crystal aligning agent of the present invention contains a heat-sensitive crosslinking agent, the content thereof is preferably 100 parts by weight or less based on 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polyorganosiloxane and other polymer optionally used And more preferably 50 parts by weight or less.

The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilyl Propyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- -Diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. And reaction products of a tetracarboxylic acid dianhydride and a silane compound having an amino group, which are described in JP-A-63-291922.

When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content thereof is preferably 50 parts by weight or more per 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polyorganosiloxane and optionally other polymer Or less, more preferably 20 parts by weight or less.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

When the liquid crystal aligning agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the liquid crystal aligning agent.

<Liquid Crystal Aligner>

As described above, the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane as an essential component and further contains other components as required. Preferably, the liquid crystal aligning agent is a liquid phase in which each component is dissolved in an organic solvent &Lt; / RTI &gt;

As the organic solvent which can be used for preparing the liquid crystal aligning agent of the present invention, it is preferable that the radiation-sensitive polyorganosiloxane and optionally other components are dissolved and not reacted with them.

The organic solvent which can be preferably used in the liquid crystal aligning agent of the present invention depends on the kind of the other polymer to which it is optionally added.

In the case where the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane, a polyamic acid and a polyimide, a preferable organic solvent used in the synthesis of a polyamic acid Include the organic solvents exemplified above. At this time, the poor solvent exemplified for use in the synthesis of the polyamic acid of the present invention may be used in combination. These organic solvents may be used alone or in combination of two or more.

On the other hand, when the liquid crystal aligning agent of the present invention contains only the radiation-sensitive polyorganosiloxane as the polymer, or when it contains the radiation-sensitive polyorganosiloxane and other polyorganosiloxane, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, di Propylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Hexyl ether, diethylene glycol, methyl Ethylcellosolve acetate, butylcellosolve acetate, methylcarbitol, ethylcarbitol, propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, acetic acid n Butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, acetic acid n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, acetic acid isoamyl and the like. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

The preferred solvent used in the production of the liquid crystal aligning agent of the present invention is one obtained by combining one or more of the above organic solvents depending on whether or not other polymers are used and the kind thereof. The components contained in the liquid crystal aligning agent are not precipitated and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.

The solid concentration of the liquid crystal aligning agent of the present invention, i.e., the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., By weight. The liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film . On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating property is sometimes insufficient. Particularly preferable ranges of the solid concentration vary depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the range of 1.5 to 4.5 wt% is particularly preferable. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9% by weight and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is in the range of 3 to 15 mPa · s accordingly.

The temperature in the production of the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, more preferably 10 ° C to 40 ° C.

&Lt; Method of forming liquid crystal alignment film &

The liquid crystal aligning agent of the present invention can be preferably used for forming a liquid crystal alignment film by a photo alignment method.

As a method for forming the liquid crystal alignment film, for example, there can be mentioned a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate, and then giving the liquid crystal aligning ability to the coating film by a photo alignment method.

First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of a substrate provided with a patterned transparent conductive film by a suitable coating method such as a roll coater method, a spinner method, a printing method, or an inkjet method, And is heated at a temperature of 250 DEG C for 0.1 to 120 minutes to form a coating film. The film thickness of the coated film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm, after removal of the solvent.

Examples of the substrate include glass such as float glass and soda glass, transparent substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate.

As the transparent conductive film, a NESA film containing SnO ₂ , an ITO film containing In ₂ O ₃ -SnO ₂ , or the like can be used. For the patterning of these transparent conductive films, a photoetching method, a method using a mask for forming a transparent conductive film, or the like is used.

In the application of the liquid crystal aligning agent, a functional silane compound, a titanate compound or the like may be previously coated on the substrate and the transparent conductive film in order to further improve the adhesion between the substrate or the transparent conductive film and the coating film.

Subsequently, the coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation, and if necessary, heat treatment is further carried out at a temperature of 150 to 250 ° C, preferably for 1 to 120 minutes, do. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction in order to impart a pretilt angle, or in combination thereof. In the case of irradiating non-polarized radiation, the irradiation direction needs to be an oblique direction.

As the light source to be used, 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 and the like can be used. The ultraviolet rays in the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter or a diffraction grating.

The irradiation dose of the radiation is preferably 1 J / m ² or more and less than 10,000 J / m ² , and more preferably 10 to 3,000 J / m ² . Further, when a liquid crystal aligning ability is imparted to a coating film formed from a conventionally known liquid crystal aligning agent by a photo alignment method, a radiation dose of 10,000 J / m ² or more is required. However, by using the liquid crystal aligning agent of the present invention, it is possible to impart favorable liquid crystal alignability even when the dose of radiation in the photo alignment method is 3,000 J / m ² or less, or even 1,000 J / m ² or less, Contribute to reduction.

The term &quot; pretilt angle &quot; in the present invention indicates the angle of the tilt of the liquid crystal molecules from the direction parallel to the substrate surface.

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element formed using the liquid crystal aligning agent of the present invention can be produced, for example, as follows.

A pair of substrates (two substrates) having the liquid crystal alignment film formed thereon as described above are prepared, and the liquid crystal alignment film therebetween is opposed so that the polarization direction of the irradiated linearly polarized radiation is at a predetermined angle, Liquid crystal is injected and filled, and the liquid crystal injection hole is sealed to constitute a liquid crystal cell. Next, it is preferable to heat the liquid crystal cell to a temperature at which the liquid crystal using isotropic phase is taken, and then cool to room temperature to remove the flow orientation at the time of injection.

Then, a polarizing plate is bonded to both sides of the polarizing plate so that the polarizing direction of the polarizing plate is at a predetermined angle with the easy axis of the liquid crystal alignment film of the substrate, thereby forming a liquid crystal display element. When the liquid crystal alignment film is horizontally oriented, the TN or STN type liquid crystal cell is formed by adjusting the angle formed by the polarization direction of the irradiated linear polarization radiation and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed Can be obtained. On the other hand, when the liquid crystal alignment film is vertically aligned, the cells are configured so that the easy axis of alignment in the two substrates on which the liquid crystal alignment film is formed is parallel, and the polarization direction of the polarizing plate is 45 degrees The liquid crystal display element having the vertical alignment type liquid crystal cell can be obtained.

As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, those having a positive dielectric anisotropy that forms a nematic liquid crystal are preferable, and examples thereof include biphenyl type liquid crystal, phenylcyclohexane type liquid crystal, ester type liquid crystal, , Biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quartz-based liquid crystal and the like. Examples of the liquid crystal include cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like can be further added to the composition.

On the other hand, in the case of the vertical alignment type liquid crystal cell, it is preferable to have a negative dielectric anisotropy for forming a nematic liquid crystal, and for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff salt mechanical liquid crystal, A liquid crystal, a biphenyl-based liquid crystal, and a phenylcyclohexane-based liquid crystal.

Examples of the polarizing plate used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state is sandwiched between cellulose acetate protective films or a polarizing plate made of the H film itself have.

The liquid crystal display element of the present invention thus manufactured is excellent in various performances such as display characteristics and reliability.

[Example]

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

The weight average molecular weight of the polyorganosiloxane in the following is the polystyrene equivalent value measured by gel permeation chromatography under the following conditions.

The solution viscosity of the polyamic acid solution was measured at 25 占 폚 using an E-type viscometer.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68 kgf / cm ²

&Lt; Synthesis of cinnamic acid derivative >

[Synthesis of the compound represented by the above formula (A-1)] [

Synthesis Example 1

Compound (A-1-C4-1) was synthesized according to the following reaction formula.

53 g of 4,4,5,5,6,6,6-heptafluorohexanol and 100 mL of pyridine were charged into a 500 mL eggplant-shaped flask and ice-cooled. To this was added dropwise a solution of 63 g of p-toluenesulfonic acid chloride in 100 mL of pyridine over a period of 30 minutes, followed by stirring at room temperature for 5 hours to carry out the reaction. After completion of the reaction, 120 mL of conc. Hydrochloric acid and 500 g of ice were added to the reaction mixture, and further ethyl acetate was added thereto. Thereafter, the organic layer was washed with water and a saturated aqueous solution of sodium hydrogencarbonate sequentially. The organic layer was dried over magnesium sulfate, then concentrated and dried to obtain 96 g of a compound (A-1-C4-1A).

Subsequently, 96 g of the above compound (A-1-C4-1A), 55 g of methyl 4-hydroxybenzoate, 124 g of potassium carbonate and 50 g of N, N-dimethylacetamide 300 mL, and the reaction was carried out by stirring at 80 DEG C for 8 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water. Subsequently, the organic layer was dried with magnesium sulfate, concentrated, and dried to obtain a white powder. 60 g of sodium hydroxide, 300 mL of water and 300 mL of tetrahydrofuran were added to the white powder, and the reaction was carried out for 24 hours under reflux. After the completion of the reaction, filtration was carried out, and then concentrated hydrochloric acid was added to the filtrate to neutralize it to form a white precipitate. This precipitate was filtered off and recrystallized from ethanol to obtain 34 g of white crystals of the compound (A-1-C4-1B).

Then, 100 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide were added to 34 g of the compound (A-1-C4-1B), and the reaction was carried out at 80 DEG C for 1 hour with stirring. Thionyl chloride was then distilled off under reduced pressure, and methylene chloride was added. The organic layer was washed with an aqueous solution of sodium hydrogencarbonate, followed by drying with magnesium sulfate, followed by concentration and then tetrahydrofuran was added.

Separately from the above, a 2 L three-necked flask was charged with 14 g of 4-hydroxycinnamic acid, 22 g of potassium carbonate, 0.96 g of tetrabutylammonium, 80 mL of tetrahydrofuran and 160 mL of water. While the solution was ice-cooled, a tetrahydrofuran solution containing a reaction product of the above compound (A-1-C4-1B) and thionyl chloride was slowly added dropwise thereto. After completion of the dropwise addition, the mixture was further stirred for 2 hours to carry out the reaction Respectively. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain a white crystal of Compound (A-1-C4-1) 19 g.

[Synthesis of Compound Represented by Formula (A-2) above]

Synthesis Example 2

Compound (A-2-C1-1) was synthesized according to the following reaction formula.

A 2 L three-necked flask equipped with a thermometer and a nitrogen inlet tube was charged with 22 g of 4-iodophenol, 16 g of hexyl acrylate, 14 mL of triethylamine, 2.3 g of tetrakistriphenylphosphine palladium and 1 g of N, N-dimethylformamide 1 L was added, and the inside of the system was sufficiently dried. Subsequently, the mixture was heated to 90 占 폚 and stirred for 2 hours under a nitrogen stream. After completion of the reaction, dilute hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, concentrated, and then subjected to column purification using a mixed solvent containing hexane and ethyl acetate, followed by concentration and drying to obtain the compound (A-2-C1-1A) 12 g was obtained.

Next, 12 g of the compound (A-2-C1-1A), 5.5 g of succinic anhydride and 0.6 g of 4-dimethylaminopyridine were introduced into a 200-mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube , And the inside of the system was sufficiently dried. Then, 5.6 g of triethylamine and 100 mL of tetrahydrofuran were added to the mixture, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate, concentrated, and then recrystallized from ethanol to obtain 8.7 g of a compound (A-2-C1-1).

&Lt; Preparation of a radiation-sensitive polyorganosiloxane >

Synthesis Example 3

5.0 g of OX-SQ (trade name, manufactured by Toagosei Co., Ltd.) as a polyorganosiloxane having an oxetane ring in a 200 mL three-necked flask, 66 g of methyl isobutyl ketone, and the compound synthesized in Synthesis Example 1 11 g of the compound (A-1-C4-1) and W-200-N alumina (trade name, manufactured by ICN Pharmaceuticals, Inc.) were added and stirred at room temperature for 48 hours, . After completion of the reaction, the precipitate was redissolved in ethyl acetate and then the precipitate was reprecipitated with methanol. The solution was washed three times with water and then the solvent was distilled off to obtain a white powder of a radiation-sensitive polyorganosiloxane (S-CO-1) 3.6 g. The weight-average molecular weight of the radiation-sensitive polyorganosiloxane (S-CO-1) was 14,500.

Synthesis Example 4

The procedure of Synthesis Example 3 was repeated except that 8 g of the compound (A-2-C1-1) synthesized in Synthesis Example 2 was used instead of the compound (A-1-C4-1) To obtain 3.0 g of a white powder of a radiation-sensitive polyorganosiloxane (S-CO-2). The weight-average molecular weight of the radiation-sensitive polyorganosiloxane (S-CO-2) was 14,200.

&Lt; Synthesis of other polymer >

[Synthesis of polyamic acid]

Synthesis Example 5

196 g (1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as a tetracarboxylic acid dianhydride and 2,2'-dimethyl-4,4'-diaminobiphenyl 212 g (1.0 mole) was dissolved in 4,050 g of N-methyl-2-pyrrolidone and the mixture was reacted at 40 占 폚 for 3 hours to obtain 3,700 g of a solution containing 10 mass% of polyamic acid (PA-1). The solution viscosity of this polyamic acid solution was 170 mPa..

[Synthesis of other polyorganosiloxane]

Synthesis Example 6

20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were put into a 200-mL three-necked flask equipped with a cooling tube, and the mixture was heated to 60 DEG C and stirred. To this was added a maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water, prepared in a separate flask having a capacity of 20 mL, and the mixture was heated and stirred at 60 DEG C for further 4 hours to carry out the reaction. The solvent was distilled off from the obtained reaction mixture, and 1-ethoxy-2-propanol was added and concentrated again to obtain a polymer solution containing 10 wt% of polyorganosiloxane (PS-1). The weight average molecular weight Mw of the polyorganosiloxane (PS-1) was 5,100.

&Lt; Preparation of liquid crystal aligning agent &

Example 1

100 parts by weight of the radiation-sensitive polyorganosiloxane S-CO-1 obtained in Synthesis Example 3 and 1,000 parts by weight (in terms of PA-1) of the solution containing the polyamic acid (PA-1) obtained in Synthesis Example 5 N-methyl-2-pyrrolidone and butyl cellosolve were added thereto, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) , And a solid content concentration of 3.0 wt%, and this was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent A-CO-1.

Example 2

The procedure of Example 1 was repeated except that the radiation sensitive polyorganosiloxane S-CO-2 obtained in Synthesis Example 4 was used instead of the radiation sensitive polyorganosiloxane S-CO-1 To prepare a liquid crystal aligning agent A-CO-2.

Example 3

The solution containing the other polyorganosiloxane (PS-1) obtained in Synthesis Example 6 was converted into PS-1 in an amount corresponding to 500 parts by weight (solids content) 100 parts by weight of polyorganosiloxane S-CO-1 was added, and 1-ethoxy-2-propanol was added to obtain a solution having a solid concentration of 4.0% by weight. Then, this solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent A-CO-3.

&Lt; Preparation and evaluation of vertical alignment type liquid crystal display device >

Example 4

The liquid crystal aligning agent A-CO-1 obtained in Example 1 was coated on the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film by using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute , And heated in an oven substituted with nitrogen at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. Subsequently, 1,000 J / m ² of polarized UV light including a bright line of 313 nm was irradiated from the direction normal to the substrate from the direction of 40 ° using an Hg-Xe lamp and a Glan Taylor prism on the surface of the coating film, . The same operation was repeated to prepare two substrates (pairs) each having a liquid crystal alignment film.

An epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 was applied to the periphery of the surface on which the liquid crystal alignment film was formed by screen printing for a pair of substrates having the liquid crystal alignment film, The substrates were superimposed on each other so that the directions were antiparallel, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a negative type liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 DEG C and then slowly cooled to room temperature. Next, a vertical alignment type liquid crystal display device was manufactured by bonding polarizers on both outer sides of the substrate so that the polarization directions thereof were orthogonal to each other and the optical axis of ultraviolet rays of the liquid crystal alignment film was at an angle of 45 degrees with respect to the substrate surface .

The liquid crystal display element was evaluated in the following manner. The results are shown in Table 1.

(1) Evaluation of liquid crystal alignment property

The presence or absence of an abnormal domain in a change in light and dark when a voltage of 5 V was turned ON / OFF (applied / released) to the liquid crystal display device manufactured as described above was observed by an optical microscope, "

(2) Evaluation of Pretilt Angle

The liquid crystal display device prepared above was described in T. J. Scheffer et. al. J. Appl. Phys. vol. 19, p. 2013 (1980)), the pretilt angle was measured by a crystal rotation method using He-Ne laser light.

(3) Evaluation of voltage holding ratio

A voltage of 5 V at 60 占 폚 was applied to the liquid crystal display device manufactured as described above at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(4) Baking

A rectangular wave of 30 Hz and 3 V, in which 5 V of DC was superimposed on the above-prepared liquid crystal display device, was applied for 2 hours at an environmental temperature of 60 캜, and then the DC voltage was cut off. After standing at room temperature for 15 minutes, The residual DC voltage was obtained by the flicker erase method.

Example 5

In the same manner as in Example 4 except that the liquid crystal aligning agent A-CO-3 prepared in Example 3 was used in place of the liquid crystal aligning agent A-CO-1 in Example 4, a vertically aligned liquid crystal display device And evaluated. The evaluation results are shown in Table 1.

Comparative Example 1

[Synthesis of polyamic acid]

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 48.46 g (0.1 mole) of a compound represented by the following formula (d-1) synthesized according to Japanese Patent Application Laid- Was dissolved in 283.4 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 67 g of polyamic acid (RPA-CO-1).

&Lt; Formula (d-1) >

&Lt; Preparation of liquid crystal aligning agent &

The polyamic acid RPA-CO-1 obtained above was dissolved in a mixed solvent consisting of N-methyl-2-pyrrolidone and butyl cellosol (mixing ratio = 50: 50 (weight ratio)) and mixed with a solution having a solid content concentration of 3.0% , And this was filtered with a filter having a pore size of 1 탆 to prepare a comparative liquid crystal aligning agent R-CO-1.

&Lt; Preparation and evaluation of vertical alignment type liquid crystal display device >

A vertical alignment type liquid crystal display device was produced and evaluated in the same manner as in Example 4 except that the liquid crystal aligning agent R-CO-1 prepared above was used in place of the liquid crystal aligning agent A-CO-1 in Example 4 Respectively. The evaluation results are shown in Table 1.

Example 6

&Lt; Preparation and evaluation of TN alignment type liquid crystal display element >

The liquid crystal aligning agent A-CO-2 prepared in Example 2 was coated on the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO film by means of a spinner and prebaked for 1 minute on a hot plate at 80 DEG C , And then heated at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. The surface of the coating film was irradiated with polarizing ultraviolet rays of 1,000 J / m ² containing a bright line of 313 nm from the normal direction of the substrate from the normal direction of the substrate by using an Hg-Xe lamp and a Glane Taylor prism, To form an alignment film. The same operation was repeated to prepare one pair (two pieces) of glass substrates having a liquid crystal alignment film on the surface of the transparent conductive film.

An epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 占 퐉 was applied to the periphery of the surface on which the liquid crystal alignment film was formed on each of the pair of substrates by screen printing and then the substrates were superimposed so that the polarizing ultraviolet ray irradiation directions were perpendicular And the adhesive was thermally cured by heating at 150 DEG C for 1 hour. Subsequently, a positive nematic liquid crystal (manufactured by Merck & Co., Inc., MLC-6221, containing a chiral agent) was injected into the gap between the substrates from the liquid crystal injection port and filled, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 for 10 minutes and slowly cooled to room temperature. The TN alignment type liquid crystal display device was manufactured by bonding polarizing plates on both outer sides of the substrate so that the polarizing directions of the polarizing plates were parallel to each other and parallel to the planar direction of the optical axis of the ultraviolet light irradiated on the liquid crystal alignment film.

The liquid crystal alignment properties, the voltage holding ratio, and the baking characteristics (residual voltage) of the liquid crystal display device were evaluated in the same manner as in Example 4 above. The results are shown in Table 1.

&Lt; Evaluation of storage stability of liquid crystal aligning agent >

Example 7

A coating film of the liquid crystal aligning agent A-CO-1 prepared in the above Example 1 was formed on the glass substrate by spin coating at a variable number of revolutions by a spin coating method, and the film thickness of the coating film after removal of the solvent was 1,000 ANGSTROM Respectively.

Subsequently, a part of the liquid crystal aligning agent A-CO-1 was taken and stored at -15 DEG C for 5 weeks. The liquid crystal aligning agent after storage was visually observed, and when the precipitation of insoluble matter was observed, the storage stability was judged as &quot; poor &quot;.

When no insoluble matter was observed after 5 weeks of storage, a coating film was formed on the glass substrate by spin coating at a revolution number of 1,000 Å before storage, and the film thickness after removal of the solvent was measured. When the film thickness was deviated by more than 10% from 1,000 Å, the storage stability was judged as "poor". When the film thickness was less than 10%, the storage stability was judged as "good".

The evaluation results are shown in Table 2.

The film thickness of the coating film was measured using an etching-type step film thickness meter manufactured by KLA-Tencor.

Examples 8 and 9

The storage stability of the liquid crystal aligning agent was evaluated in the same manner as in Example 7 except that the liquid crystal aligning agent described in Table 2 was used in place of the liquid crystal aligning agent A-CO-1 in Example 7.

The evaluation results are shown in Table 2.

As is clear from the above examples, the liquid crystal aligning agent containing the radiation-sensitive polyorganosiloxane of the present invention is free from the rubbing treatment and has excellent liquid crystal alignability, good pretilt It is possible to obtain a liquid crystal alignment film which exhibits excellent electrical characteristics. The liquid crystal display device comprising the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is remarkably improved in the baking characteristics compared with the polyimide having the known cinnamic acid derivative in the side chain.

Therefore, when a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than the conventional one, and various performances such as display characteristics and reliability are excellent. Therefore, these liquid crystal display elements can be effectively applied to various apparatuses and can be suitably used for apparatuses such as a desk calculator, a wrist watch, a desk clock, a coefficient display board, a word processor, a personal computer, a liquid crystal television, and the like.

Claims (7)

Having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ and -SO ₂ Cl Namsan derivatives,
A polyorganosiloxane having an oxetane ring
Wherein the liquid crystal aligning agent contains a radiation-sensitive polyorganosiloxane. The liquid crystal aligning agent according to claim 1, wherein the cinnamic acid derivative is a compound represented by the following formula (A-1) or a compound represented by the following formula (A-2).
&Lt; Formula (A-1) >

(In the formula (A-1), R ¹ is a monovalent organic group having 3 to 40 carbon atoms and containing an alkyl group having 1 to 40 carbon atoms or an alicyclic group, provided that a part or all of the hydrogen atoms of the alkyl group are substituted with a fluorine atom R ² is a single bond, an oxygen atom, -COO- or -OCO-, R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R ⁴ represents a single bond, an oxygen atom, -COO- or -OCO-, and R ⁵ represents a single bond, a methylene group, a group of 2 to 10 carbon atoms alkyl group or an aromatic divalent group, R ⁵ a is a single bond when R ⁶ is a hydrogen atom, R ⁵ is a methylene group, an alkylene group or a divalent aromatic group, when R ⁶ is a carboxyl group, a hydroxyl group, -SH, -NCO, It is -NHR, -CH = CH ₂ or -SO ₂ Cl, but with R 1 a hydrogen atom or a carbon atoms in An alkyl group of 6, R ⁷ is a fluorine atom, a methyl group or a cyano group, a is an integer from 0 to 3, b is an integer of from 0 to 4)
&Lt; General Formula (A-2) >

(In the formula (A-2), R ⁸ is a monovalent organic group having 3 to 40 carbon atoms, which is an alkyl group having 1 to 40 carbon atoms or an alicyclic group or an aromatic group, provided that a part or all of the hydrogen atoms of the alkyl group is a fluorine atom and so may be substituted, R ⁹ is a single bond, an oxygen atom, -COO- or -OCO-, R ¹⁰ is a methylene group, an alkylene group, having 2 to 10 carbon atoms a divalent aromatic group, a divalent alicyclic group, a divalent R ¹¹ is a single bond, -OCO- (CH ₂ ) _e -, - (CH ₂ ) _e -, or a bivalent fused ring group, provided that at least one hydrogen atom of the bivalent aromatic group may be substituted with a fluorine atom, (CH ₂ ) _g - or -O- (CH ₂ ) _i -, e, g and i are each an integer of 1 to 10, R ¹² is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR , and -CH = CH ₂ or -SO ₂ Cl, but wherein R is a hydrogen atom or an alkyl group having 1 to 6, R ¹³ is a fluorine atom, a methyl group or a cyano Group and, c is an integer from 0 to 3, d is an integer of from 0 to 4) The polyorganosiloxane according to claim 1 or 2, wherein the polyorganosiloxane is a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof, and a condensate of a hydrolyzate. Liquid crystal aligning agent.
&Lt; Formula (S-1) >

(In the formula (S-1), X is a monovalent organic group having a structure represented by the following formula (X-1), Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms
&Lt; Formula (X-1) >

(In the formula (X-1), R ¹⁴ is an alkyl group having 1 to 6 carbon atoms, and "*" The liquid crystal aligning agent according to claim 1 or 2, further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide. The positive resist composition according to Claim 1 or 2, which further comprises at least one member selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (S-2), a hydrolyzate thereof and a condensate of a hydrolyzate The liquid crystal aligning agent.
&Lt; Formula (S-2) >

(Wherein R ¹⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, Y ² is a hydroxyl group, a halogen atom, an alkoxyl group having 1 to 20 carbon atoms, 1 to 6 alkyl group) A method for forming a liquid crystal alignment film, comprising applying a liquid crystal aligning agent according to claim 1 or 2 on a substrate to form a coating film, and irradiating the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 1 or 2.