KR101512212B1 - Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

(화학식 1 중, R¹, R² 및 R³은 각각 독립적으로 수소 원자 또는 1가의 유기기이되, 단 R³이 수소 원자가 아닌 경우에는 R¹ 및 R² 중 1개 이상은 카르복실기 또는 카르복실기를 갖는 유기기이고, R¹과 R²는 서로 결합하여 환을 형성할 수도 있음)The present invention relates to a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane obtained by reacting a compound represented by the following formula (1) with a polyorganosiloxane having an epoxy group.
≪ Formula 1 >

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group, provided that when R ³ is not a hydrogen atom, at least one of R ¹ and R ² has a carboxyl group or a carboxyl group And R < ¹ > and R < ² > may be bonded to each other to form a 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, a liquid crystal alignment material,

The present invention relates to a liquid crystal aligning agent, a method for forming a liquid crystal alignment film, and a liquid crystal display element.

Conventionally, a nematic liquid crystal having a positive dielectric anisotropy is made into a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and TN (Twisted) structure in which long axes of liquid crystal molecules are continuously twisted (JP-A-56-91277 and JP-A-2005-34712) are known which have liquid crystal cells such as Nematic type, STN (Super Twisted Nematic) type, IPS (In Plane Switching) type, 1-120528).

In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align the liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the substrate surface with a cloth member such as rayon in one direction. However, when a liquid crystal alignment film is formed by rubbing treatment, since dust and static electricity are liable to be generated in the process, dust adheres to the surface of the alignment film, which causes a problem of display failure. 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 expected to be further higher-density in the future, irregularities are unavoidably generated on the surface of the substrate due to high density of pixels, so that it is difficult to uniformly perform the rubbing process.

As another means for orienting the liquid crystal in the liquid crystal cell, a method of irradiating polarized light or non-polarized light to a photosensitive thin film such as polyvinyl cinnamate, polyimide or azobenzene derivative formed on the substrate surface, The orientation method is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (Japanese Patent Application Laid-Open Nos. 6-287453, 10-251646, 11-2815, 11-152475, 2000-144136, 2000-319510, 2000-281724, and 2000-281724, 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. When a liquid crystal alignment film is formed by the photo alignment method, the pretilt angularity is usually imparted by irradiating the incident direction of the substrate with respect to the substrate surface, which is inclined from the substrate normal.

On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are vertically oriented on a substrate is also known as an operation mode of the liquid crystal display device separate from the above. In this operation mode, when a voltage is applied between the substrates to tilt the liquid crystal molecules toward a direction parallel to the substrate, it is necessary that the liquid crystal molecules are inclined from one direction of the substrate normal to one direction within the substrate surface. As a means for this purpose, 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 rubbing the liquid crystal molecules toward the substrate normal direction And the like) have been proposed.

It is known that the photo alignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in the liquid crystal cell of the vertical alignment mode. That is, it has been known that the use of a vertical alignment film imparting alignment control ability and pretilt angle manifestation by a photo alignment method enables uniform control of the tilt direction of liquid crystal molecules upon voltage application (JP-A-2003-307736 Japanese Patent Laid-Open Nos. 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 radiation dose necessary 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, its optical axis must be irradiated with 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, p. 579).

Therefore, a liquid crystal aligning agent containing a polymer having a group derived from cinnamic acid in its side chain has been studied in order to provide good liquid crystal aligning ability and pretilt angularity in a liquid crystal alignment film obtained even at a low radiation dose Japanese Unexamined Patent Publication (Kokai) No. 6-287453). This technique relates to a liquid crystal aligning agent containing a polymer synthesized using a cinnamic acid derivative having an alkoxyl group. Since the coating film of this liquid crystal aligning agent has absorption in a long wavelength region of 365 nm or more, for example, in a visible light region In addition to a photo alignment process for forming a liquid crystal alignment film, a photoreaction is also caused by, for example, an ultraviolet curing process of a sealant at the time of manufacturing a liquid crystal panel or light of a back light, thereby causing problems in the liquid crystal orientation and reliability of the panel.

It is also conceivable to use the cinnamic acid derivative having an ester group in place of the alkoxyl group to shift the absorption spectrum toward the shorter wavelength side to solve the above problems. However, according to this technique, there is no possibility that pyrolysis of the side chain of the cinnamic acid derivative occurs at the time of post-baking in the liquid crystal panel manufacturing process, and there is a possibility that the substrate or panel production line may be contaminated.

As described above, it is possible to form a liquid crystal alignment film having good liquid crystal aligning ability, excellent electric characteristics, and high heat resistance by a photo alignment method with a small radiation dose, and it is possible to provide a liquid crystal alignment film having a problem of thermal decomposition during post- A liquid crystal aligning agent which does not cause a problem of photodecomposition has hitherto not been known.

The object of the present invention is to provide a liquid crystal alignment film excellent in storage stability and having good liquid crystal aligning ability even at a low exposure dose by irradiation with polarized light or unpolarized light without rubbing treatment A method of forming a liquid crystal alignment film excellent in electrical characteristics and heat resistance using the liquid crystal aligning agent and a liquid crystal display device having excellent performance such as display characteristics and reliability, And the like.

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

A compound represented by the following formula (1)

At least one member 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

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

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group, provided that when R ³ is not a hydrogen atom, at least one of R ¹ and R ² has a carboxyl group or a carboxyl group And R < ¹ > and R < ² > may be bonded to each other to form a ring)

[S-1]

(In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group and Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms)

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 onto 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-mentioned liquid crystal aligning agent.

According to the present invention, it is possible to provide a liquid crystal alignment film excellent in storage stability and having good liquid crystal aligning ability even at a low exposure dose by irradiating with polarized light or unpolarized light without rubbing treatment, It is possible to obtain a liquid crystal display element excellent in various performances such as a liquid crystal aligning agent having no absorption for the liquid crystal alignment agent, a method for forming a liquid crystal alignment film excellent in electric characteristics and heat resistance using the liquid crystal aligning agent, and display characteristics and reliability.

The liquid crystal aligning agent of the present invention can be produced by reacting a compound represented by the formula (1) (hereinafter referred to as "cinnamic acid derivative (1)")

(Hereinafter referred to as "polyorganosiloxane having an epoxy group") selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (S-1), a hydrolyzate thereof and a condensate of a hydrolyzate,

To obtain a radiation-sensitive polyorganosiloxane.

≪ Synnamic acid derivative (1) >

The cinnamic acid derivative (1) used in the present invention is a compound represented by the above formula (1). R ¹ and R ² in the above formula (1) are each a hydrogen atom, or an oxygen atom, a sulfur atom or a divalent group -NR- (provided that R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Or an aliphatic group having 1 to 40 carbon atoms or an alicyclic group having 3 to 40 carbon atoms. These aliphatic groups or alicyclic groups may be substituted by fluorine atoms. When R ³ is not a hydrogen atom, at least one of R ¹ and R ² is a carboxyl group, an aliphatic group or an organic group in which a part (preferably one) of hydrogen atoms of the alicyclic group is substituted by a carboxyl group to be.

The ring when R ¹ and R ² are bonded to each other to form a ring is, for example, a monocyclic ring having 3 to 8 carbon atoms, a condensed ring having 4 to 40 carbon atoms, a bridged ring having 4 to 40 carbon atoms, And may be a crosslinked condensed ring of 5 to 40 carbon atoms. At this time, the total number of carbon atoms of R ¹ and R ² is preferably 6 to 40. When R ³ is not a hydrogen atom, the ring is a monocyclic, condensed ring, crosslinked ring or crosslinked condensed ring having a carboxyl group. When the ring is a monocyclic ring, a bridged ring or a condensed ring condensed ring, it is preferably an alicyclic ring. When the ring is a condensed ring, it may be a condensed ring of an alicyclic ring and an alicyclic ring or a condensed ring of an alicyclic ring and an aromatic ring. When the ring is a condensed ring of an alicyclic ring and an aromatic ring, the ring condensed with the imide ring is preferably an alicyclic ring.

R ³ in Formula 1 is preferably a hydrogen atom, - (CH ₂ ) _a -COOH, -C _b H _{2b +1} , - (CH ₂ ) _c --C _d F _{2d + 1} B is an integer of 4 to 20, c is an integer of 0 to 18, and d is an integer of 1 to 18), a cholesteryl group or a cholestanyl group.

The cinnamic acid derivative (1) is preferably a compound represented by the following formula (2) or a compound represented by the following formula (3).

(Wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group, provided that at least one of R ⁴ and R ⁵ is an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom or a fluorine atom And R < ⁴ > and R < ⁵ > may be bonded to each other to form a ring)

(Wherein R ⁶ is a single bond or a divalent organic group; R ⁷ is a hydrogen atom or a monovalent organic group; R ⁶ and R ⁷ may be bonded to each other to form a ring; and R ⁸ is a fluorine atom An alkyl group having 1 to 20 carbon atoms which may be substituted or an alicyclic group having 3 to 40 carbon atoms which may be substituted with a fluorine atom)

Preferred examples of the compound represented by the formula (2) include compounds represented by the following formula (2-1) wherein R ⁴ and R ⁵ are not bonded to each other;

R ⁴ and R ⁵ bond to each other to form a monocyclic ring, and examples thereof include compounds represented by the following formulas (2-2) and (2-3);

R ⁴ and R ⁵ are bonded to each other to form a condensed ring, for example, a compound represented by the following formula (2-4);

Examples of the compound represented by the following formula (2-5) to (2-10) include those in which R ⁴ and R ⁵ are bonded to each other to form a crosslinked ring.

(Wherein R ⁹ , R ¹¹ , R ¹³ and R ¹⁵ are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom or an alicyclic group having 3 to 40 carbon atoms which may be substituted with a fluorine atom and R ¹⁰ An oxygen atom, a sulfur atom or a divalent group -COO-, -OCO- or -NR- (wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), R ¹² is a divalent group -COO -, -OCO-, -COS-, -SCO-, -CONR- or -NRCO- (wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), R ¹⁴ is a single bond, an oxygen atom or a divalent -O-CH ₂ -, -CH ₂ -O-, -COO- or -OCO-, R ¹⁶ represents a single bond, an oxygen atom, a sulfur atom or a divalent group -COO-, -OCO-, -COS- Or -SCO-)

As R ⁹ in the above formula (2-1), a straight chain alkyl group having 4 to 20 carbon atoms is preferable, and as R ¹⁰ , a single bond, an oxygen atom or a sulfur atom is preferable.

Examples of R ¹¹ in the above formula (2-2) include straight-chain alkyl groups having 4 to 20 carbon atoms, a cholesteryl group, a cholestanyl group, an adamantyl group, a 4-amylcyclohexyl group or a 4- A butylcyclohexyl group is preferable, and as R ¹² , a divalent group -COO- or -OCO- is preferable.

As R ¹³ in the above formula (2-3), a straight chain alkyl group having 4 to 20 carbon atoms which may be substituted with a fluorine atom, a cholesteryl group, a cholestanyl group, an adamantyl group, a 4-amylcyclohexyl group or a 4-butylcyclo A hexyl group is preferred.

R ¹⁵ in the formulas (2-4) to (2-9) is preferably a straight chain alkyl group of 4 to 20 carbon atoms which may be substituted with fluorine, and R ¹⁶ is preferably a single bond.

More specific examples of the compound represented by the above formula (2) include compounds represented by the above formula (2-1), for example, compounds represented by the following formulas (2-1-1) to (2-1-3) My back;

Examples of the compound represented by the above formula (2-2) include compounds represented by the following formula (2-2-1), and the like.

(Wherein R ⁹ and R ¹¹ are the same as those in the formula (2-1) or (2-2), respectively)

The compound represented by the formula (2) can be synthesized by an organic chemical method.

For example, the compound represented by the above formula (2-1) can be obtained by, for example, a method of refluxing a derivative of succinic anhydride having the group R ⁹ -R ¹⁰ - and 4-aminocinnamic acid in acetic acid, Sulfuric acid, or triethylamine in the presence of a suitable catalyst. 4-iodophenylmaleimide was synthesized from 4-iodoaniline and maleic anhydride in the same manner as described above, and then the group R ⁹ -R ¹⁰ - was introduced by Michael addition, The compound represented by the above formula (2-1) can be obtained by a reaction.

Among the compounds represented by the above general formula (2-2), for example, a compound in which a divalent group R ¹² is * -OCO- (in which a bond with "*" is bonded to R ¹¹ ) The product obtained by reacting hydrogenated trimellitic anhydride with an acid chloride by thionyl chloride and then reacting the compound with R ¹¹ -OH in the presence of a suitable base such as triethylamine to form an ester bond is named 4 - < / RTI > amino cinnamic acid. In this case, the reaction between the esterified compound and 4-aminocinnamic acid can be carried out under the same conditions as in the case of the compound represented by the formula (2-1).

The compound represented by the above formula (2-3) can be obtained by reacting a compound obtained by reacting maleic anhydride with a styrene derivative by using N-nitrosophenylhydroxyamine aluminum salt and hydroquinone as a catalyst, and 4- Can be obtained by reacting aminocinnamic acid in the same manner as in the synthesis of the compound represented by the formula (2-1).

Among the compounds represented by the above general formula (2-4), for example, the compound wherein R ¹⁶ is a single bond can be obtained by, for example, reacting a 5-position substituted cyclopentadiene having a group R ¹⁵ - at the 5-position with a maleic anhydride, By the Diels-Alder reaction, and then reacting the adduct and 4-aminocinnamic acid in the same manner as in the synthesis of the compound represented by the formula (2-1). Here, the 5-position substituted cyclopentadiene having the group R ¹⁵ - at the 5-position is reacted with an excessive amount of the compound R ¹⁵ -X (wherein X is a halogen atom) with respect to the cyclopentadienyl anion at -20 to 30 ° C Can be obtained by preference.

Of the compounds represented by the above formula (2-5), for example, a compound wherein R ¹⁶ is a single bond is a compound wherein a 1-position substituted cyclopentadiene having a group R ¹⁵ - at position 1 is used instead of a 5-position substituted cyclopentadiene Can be synthesized by the same method as in the synthesis of the compound represented by the above general formula (2-3). Here, the 1-position substituted cyclopentadiene having the group R ¹⁵ - at the 1-position is a cyclopentadienyl compound having a cyclopentadienyl group in which the compound R ¹⁵ -X (wherein X is a halogen atom) in an amount of 0.8 to 1.2 equivalents based on 1 equivalent of the cyclopentadienyl anion is -78 To < RTI ID = 0.0 > 20 C. < / RTI >

Preferred examples of the compound represented by the above formula (3) include compounds represented by the following formula (3-1) wherein R ⁶ and R ⁷ are not bonded to each other;

R ⁶ and R ⁷ are bonded to each other to form a monocyclic ring, for example, a compound represented by the following formula (3-2);

And R ⁶ and R ⁷ are bonded to each other to form a condensed ring, for example, a compound represented by the following formula (3-3).

(Wherein R ⁸ has the same meaning as in formula (3), R ¹⁷ is a methylene group or an alkylene group having 2 to 10 carbon atoms, R ¹⁸ is an oxygen atom, a sulfur atom or a divalent group -COO-, - OCO- or -NR- (wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)

More specific examples of the compound represented by the formula (3) include compounds represented by the formula (3-2-1), for example, as the compound represented by the formula (3-2).

(Wherein R ⁸ has the same meaning as in the above formula (3-2), and a is an integer of 1 to 10)

In the above formula (3-1), for example, a compound wherein the group R ¹⁸ is a sulfur atom can be obtained by, for example, Michael addition of a compound HOOC-R ¹⁷ -SH to 4-iodophenylmaleimide, ₂ = CH-COOR ⁸ with a Heck reaction.

The compound represented by (3-2-1) among the compounds represented by the above formula (3-2) can be prepared by, for example, reacting 4-nitrocinnamic acid with a halogenated alkyl having an alkyl group corresponding to R ¹ in the presence of potassium carbonate, Reacted to give an ester, the nitro group thereof is reduced with, for example, tin chloride to obtain an amino group, 4-aminocinnamic acid ester is obtained, and the resulting product is reacted with 1,2,4-tricarboxycyclohexylcyclohexane anhydride . The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine.

The compound represented by the above formula (3-3) can be obtained by, for example, using N-nitrosophenylhydroxyamine aluminum salt and hydroquinone as catalysts and heating maleic anhydride and 4-vinylbenzoic acid to react Can be obtained by reacting the 4-aminocinnamic acid ester prepared in the same manner as in the synthesis of the compound and the compound represented by the formula (3-2-1) in the same manner as in the formula (2-1).

<Polyorganosiloxane Having Epoxy Group>

The polyorganosiloxane having an epoxy group used in the present invention is at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (S-1), a hydrolyzate thereof and a condensate of a hydrolyzate.

As X ¹ in the above-mentioned polyorganosiloxane having an epoxy group, a group represented by the following formula (X ¹ -1) or (X ¹ -2) is preferable.

Examples of the alkoxyl group having 1 to 10 carbon atoms represented by Y ¹ include a methoxyl group and an ethoxyl group; Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like; Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and the like.

The polyorganosiloxane having an epoxy group 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 5,000 desirable.

The polyorganosiloxane having an epoxy group is preferably obtained by subjecting a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound to hydrolysis or hydrolysis in the presence of an appropriate organic solvent, And can be synthesized by condensation.

Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (Trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyl tri-n-butoxysilane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- N-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- (Perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (Perfluoro-n-octyl) ethyl tri-n-octyl) ethyl tri-i-propoxysilane, 2- (perfluoro- Tri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propyl (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri- (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3- Propyl tri-sec-butoxysilane, mercaptomethyl trimethoxysilane, mercaptomethyl triethoxysilane, vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane , Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri- Butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, propoxy silane, phenyl tri-n-butoxy silane, phenyl tri-sec-butoxy silane, methyldichlorosilane, Methyldimethoxysilane, methyldiethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi- sec-butoxysilane, dimethyldichlorosilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) 2- (perfluoro- Octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (Methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di- (Methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dichlorosilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (Methyl) (vinyl) di (vinyl) di (vinyl) di (meth) acrylate, (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi n-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Propoxy silane, diphenyl di-i-propoxy silane, diphenyl di-n-butoxy silane, diphenyl di-sec-butoxysilane, Silane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, In addition to a silane compound having one silicon atom such as (methoxy) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane and (ethoxy)

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 Shinetsu Chemical Industry 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 GR950 (manufactured by Showa Denko K.K.).

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltri But are not limited to, ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, or dimethyldiethoxysilane are preferable.

The polyorganosiloxane having an epoxy group used in the present invention preferably has an epoxy equivalent of 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, it is preferable to adjust and set the epoxy equivalent of the polyorganosiloxane to obtain the ratio of the silane compound having an epoxy group and the other silane compound to the above range.

Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbon, ketone, ester, ether, alcohol and the like.

Examples of the hydrocarbon include toluene, xylene and the like;

Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like;

Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like;

Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;

Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, non-water-soluble ones are preferable.

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

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 preparing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times by mole, more preferably 1 to 30 times by mole based on the total amount of the silane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound and the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst for producing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing a side reaction such as ring opening of an epoxy group, . Further, the liquid crystal aligning agent of the present invention containing a reactant of a polyorganosiloxane having an epoxy group synthesized by using an alkali metal compound or an organic base as a catalyst and a cinnamic acid derivative (1) is preferable because of excellent storage stability . As pointed out in the literature [Chemical Reviews, Vol. 95, p. 1409 (1995)], when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, Or a cage structure is formed, and a polyorganosiloxane having a small content of silanol groups is obtained. The condensation reaction between the silanol groups is suppressed because the content of the silanol group is small. Further, when the liquid crystal aligning agent of the present invention contains the other polymer described later, the condensation reaction of the silanol group and the other polymer is inhibited, It is presumed that the stability is excellent.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used varies depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and should be appropriately set. For example, the amount is preferably 0.01 to 3 times, 1 times the moles.

The hydrolysis or hydrolysis and condensation reaction in the production of a polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, mixing the solution with an organic base and water For example, by heating in a hot water bath or the like.

In the hydrolysis and condensation reaction, the heating temperature is preferably 130 ° C or less, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, and more preferably 1 to 8 hours . During the heating, the mixed solution may be stirred or may be kept under reflux.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, it is preferable that the cleaning operation is facilitated by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt%. The washing is carried out until the water layer after the washing becomes neutral. Thereafter, the organic solvent layer is dried with an appropriate drying agent such as calcium sulfate anhydride or molecular sieve, if necessary, and then the solvent is removed to obtain a desired polyorganosiloxane having an epoxy group Can be obtained.

In the present invention, a commercially available polyorganosiloxane having an epoxy group may also be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21 and EMS-32 (manufactured by Chisso Corporation).

<Radiation-sensitive polyorganosiloxane>

The radiation-sensitive polyorganosiloxane used in the present invention can be synthesized by reacting a polyorganosiloxane having an epoxy group as described above with a cinnamic acid derivative (1), preferably in the presence of a catalyst. The cinnamic acid derivative (1) is used in an amount of preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more preferably 0.05 to 0.9 mol based on 1 mol of the epoxy group of the polyorganosiloxane.

As the catalyst, there can be used an organic base or a compound known as a so-called curing accelerator which promotes the reaction between an epoxy compound and an acid anhydride.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;

2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) 1- (2-cyanoethyl) -2-n-octylimidazole, 1- (2-cyanoethyl) 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- (2-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- (2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl- Triazine, 2,4-di Amino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine; Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphate;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor Butylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra- Quaternary phosphonium salts such as tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

High melting point dispersing type latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amines and epoxy resins;

A microcapsulated latent curing accelerator wherein the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing accelerator;

And latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Among these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane having an epoxy group.

The reaction temperature is preferably 0 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The synthesis reaction of the radiation-sensitive polyorganosiloxane can be carried out in the presence of an organic solvent if necessary. Examples of such an organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, and an alcohol compound. Of these, ether compounds, ester compounds and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent is used in such an amount that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight.

The radiation sensitive polyorganosiloxane of the present invention introduces a structure derived from a cinnamic acid derivative (1) by a ring-opening addition of an epoxy into a polyorganosiloxane having an epoxy group. This production method is not only simple but also highly preferable in that it can increase the introduction rate of the structure derived from the cinnamic acid derivative.

In the synthesis of the radiation-sensitive organopolysiloxane of the present invention, a part of the cinnamic acid derivative may be substituted by a compound represented by the following general formula (4) within a range not to impair the effect of the present invention. In this case, the synthesis of the radiation-sensitive polyorganosiloxane is carried out by reacting a mixture of a polyorganosiloxane having an epoxy group with a cinnamic acid derivative and a compound represented by the following formula (4).

(In the general formula (4), R ¹⁹ is an alkyl group or alkoxyl group having 4 to 20 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, provided that a part or all of the hydrogen atoms of the alkyl group or alkoxyl group is a fluorine atom R ²⁰ is a monovalent or phenylene group, provided that when R ¹⁹ is an alkoxyl group, R ²⁰ is a phenylene group and Z is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR A hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH _2, and -SO ₂ Cl.

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

Specific examples of the compound represented by the formula (4) include compounds represented by the following formulas (4-1) to (4-4).

(4-1) wherein f is an integer of 1 to 10, g is an integer of 0 to 5, h in the formula (4-2) is an integer of 5 to 20, 3), i is an integer of 1 to 3, j is an integer of 0 to 18, and k in the formula (4-4) is an integer of 1 to 18)

Specific examples of the compound represented by the formula (4) include dodecanoic acid, stearic acid, and compounds represented by the following formulas (4-3-1) to (4-3-3).

The compound represented by Formula 4 is reacted with a polyorganosiloxane having an epoxy group together with the cinnamic acid derivative (1) under the same reaction conditions as the cinnamic acid derivative (1) and introduced into the photosensitive polyorganosiloxane, To give a pretilt angle expression. In the present specification, the compound represented by Formula 4 is hereinafter referred to as "another pretilt angle-expressing compound".

The compound represented by the formula (4) may be used in an amount of preferably 50 mol% or less, more preferably 33 mol% or less based on the total amount of the cinnamic acid derivative (1) and the compound represented by the formula (4). If the proportion of the compound represented by the formula (4) exceeds 50 mol%, there is a problem that an abnormal domain occurs when the obtained liquid crystal display element is turned ON (voltage applied state).

<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 a polymer other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as "another polymer"), a curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule Epoxy compound "), a functional silane compound, and a surfactant.

<Other Polymers>

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 resulting liquid crystal alignment film. Examples of such another polymer include at least one polymer selected from the group consisting of a polyamic acid and a polyimide, a polysiloxane represented by the following formula (S-2), a hydrolyzate thereof and a hydrolyzate condensate Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be used in combination with one or more of the above-mentioned polysiloxanes (hereinafter referred to as "other polysiloxane"), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, .

[Formula S-2]

(In the formula (S-2), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Y ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms Practical skill)

[Polyamic acid]

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

Examples of the tetracarboxylic acid dianhydride which can be used for the synthesis of polyamic acid include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro- 3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo Pentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5 - tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a , 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro- 3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- ( 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7,7-dihydro- -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] 3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- furanyl) -naphtho [ Dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene- Tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dicarboxylic acid anhydride, bicyclo [2.2.2] (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- Dicarboxylic acid anhydride, 3,5,6-tricarboxy- ^2- carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2 , 6} ] undecane-3,5,8,10-tetraone, compounds represented by each of the following formulas (TI) and (T-II), and alicyclic or alicyclic tetracarboxylic acid dianhydride;

(Formula (TI) and (T-II) of, R ²¹ and R ²² is a divalent organic group having each an aromatic ring, R ²³ and R ²⁴ are each a hydrogen atom or an alkyl group, R ²³ and R to a plurality of presence ²⁴ may be the same or different from each other)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5 , 8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxyl 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 dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3' '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) dianhydride, m-phenylene- (Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydroglycidyl) Bis (4-hydroxyphenyl) propane-1,6-hexanediol-bis (anhydrotrimellitate) Aromatic tetracarboxylic acid dianhydrides such as bis (anhydrotrimellitate) and compounds represented by the following formulas (T-1) to (T-4). These may be used singly or in combination of two or more.

Among them, preferred are butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetra 2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2 ] Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione- 3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, 3 (3-methyl-3-furyl) , 5,6-tricar Diplopia-2-carboxy-norbornane 2: 3,5: 6-dianhydride, 4,9- dioxa-tricyclo [5.3.1.0 ^2,6] undecane -3,5,8,10- tetrahydro-one, Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 2,2 ' (T-5) to (T) in the compound represented by the above formula (TI), a compound represented by the formula -7) and the compound represented by the formula (T-8) in the compound represented by the formula (T-II) are preferable from the viewpoint of being able to exhibit good liquid crystal alignability.

Particularly preferred are 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1 (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3- 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6- dianhydride, 4,9- Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-5).

Examples of the diamine used for the synthesis of the 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, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl , 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Bis (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1 (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diamino Fluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'- ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, Dimethoxybiphenyl, 1,4,4 '- (p-phenyleneisopropylidene) bisaniline, 4,4' - (m-phenyleneisopropylidene) bisaniline, 2 , 2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) Phenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, Aromatic diamines such as compounds represented by the following formulas (D-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)

But are not limited to, 1,1-hexanediol, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Tetradecylenediamine diamine, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanedanilinedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenediethylenediamine, 4,4'methylenebis ( Cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and other aliphatic or alicyclic diamines;

Diaminopyridine, 5, 6-diamino-2,3-dicyanopyrimidine, 5, 6-diamino-2,3-dicyanopyrimidine, Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridactate, 3,8-diamino-6-phenylphenanthridine, Aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl- Aminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, a compound represented by the following formula (DI) A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound to be displayed;

(In the formula (DI), R ²⁵ is a monovalent organic group having a ring structure including a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, X ³ is a divalent R ²⁶ is an alkyl group having 1 to 4 carbon atoms, a 1 is an integer of 0 to 3, and when a plurality of R ^{26 s} exist, they may be the same or different)

(In the formula (D-II), R ²⁷ is a divalent organic group having a ring structure including a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, and X ⁴ is Each R ² is an alkyl group having 1 to 4 carbon atoms, a 2 is an integer of 0 to 4, each of X ^{2 s} present may be the same as or different from each other, and when a plurality of R ^{2 s} are present Each of which may be the same or different)

A mono-substituted phenylenediamine represented by the following formula (D-III);

(Formula (D-III) of, R ²⁹ is -O-, -COO-, -OCO-, -NHCO-, -CONH- , and a divalent organic group selected from the group consisting of -CO-, R ³⁰ is A monovalent organic group having a steroid skeleton, a monovalent organic group having a trifluoromethylphenyl group, a trifluoromethoxyphenyl group or a phenylphenyl group, or an alkyl group having 6 to 30 carbon atoms, R ³¹ is an alkyl group having 1 to 4 carbon atoms, a3 Is an integer of 0 to 3 and may be the same or different when plural R ³¹ are present)

A diaminoorganosiloxane such as a compound represented by the following formula (D-IV), and the like. These diamines may be used alone or in combination of two or more.

(Wherein R ³² is a hydrocarbon group having 1 to 12 carbon atoms, plural R ^{32 s} present may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 3, 20)

The benzene ring of the aromatic diamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). R ²⁶ , R ²⁸ and R ³¹ in formulas (DI), (D-II) and (D-III) are preferably methyl groups, and a1, a2 and a3 are each preferably 0 or 1, 0 &lt; / RTI &gt;

The monovalent organic group having a steroid skeleton at R ³⁰ of the above formula (D-III) preferably has 17 to 51 carbon atoms, more preferably 17 to 30 carbon atoms. Specific examples of R ³⁰ having a steroid skeleton include a cholestan-3-yl group, a cholesta-5-en-3-yl group, a cholesta-24- 3-yl group, and lanostan-3-yl group.

Of these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'- Diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2'- Bis [4- (4-aminophenoxy) phenyl] hexafluoro-2,2-bis [4- Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - (m-phenylenediisopropylidene) bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-cyclohexanediamine, 4,4'-methylenebis Amines), 1,3-bis (aminomethyl) cyclohexane, compounds represented by the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4- , 4-diaminopyrimidine , 3,6-diamino acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, (D-6), the compound represented by the formula (D-6), the compound represented by the formula (D-6) (D-7) among the compounds represented by the formula (II-II), the dodecanoxy-2,4-diaminobenzene, the pentadecanoxy-2,4 -Diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-di (D-8) to (D-16) shown below and a compound represented by the formula (D-8) (3-aminopropyl) -tetra (IV) &lt; / RTI &gt; The tildi siloxane is preferred.

The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the amino group contained in the diamine, More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 to 150 ° C, more preferably 0 to 100 ° C for preferably 1 to 48 hours, more preferably 2 to 10 hours Lt; / RTI &gt; 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 used in combination with the following poor solvent) means that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is less than the total amount + b) is preferably from 0.1 to 30% by weight.

The organic solvent may be used in combination with alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon or the like generally known as a poor solvent for the polyamic acid so long as the produced polyamic acid is not precipitated. Specific examples of such a poor solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, Butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl Ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol 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, isoamyl propionate, isoamyl isobutylate, and diisopentyl ether.

When a poor solvent as described above is used in combination with an organic solvent in the production of polyamic acid, the use ratio thereof can be appropriately set within a range in which the produced polyamic acid is not precipitated, but preferably 50% By weight, and more preferably 20% by weight or less.

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be used as it is for preparing a liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and used for the preparation of a liquid crystal aligning agent, or after the isolated polyamic acid is purified, . The isolation of the polyamic acid can be carried out by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by 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 synthesized by imidizing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine by dehydration ring closure.

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyimide include the same compounds as the tetracarboxylic dianhydride used in the synthesis of the polyamic acid described above.

As the tetracarboxylic acid dianhydride used in the synthesis of the polyimide usable in the present invention, a tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride is preferably used. Particularly preferred alicyclic tetracarboxylic acid dianhydrides include 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra Furanyl) -naphtho [l, 2-c] furan-l, 3-dione, 3-oxabicyclo [3.2.1] octane- (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl- Dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride or 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraone.

In the synthesis of the polyimide, alicyclic tetracarboxylic dianhydride and other tetracarboxylic dianhydride may be used in combination. In this case, the proportion of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 10 mol% or more, and more preferably 50 mol% or more.

Examples of the diamine used in the synthesis of the polyimide include the same compounds as the diamines used in the synthesis of the polyamic acid described above.

As the diamine used in the synthesis of the polyimide of the present invention, it is preferable to use a diamine containing a diamine represented by the above formula (D-III). As specific preferred examples of the compound represented by the above formula (D-III), dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy- Diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy- , Octadecaneoxy-2,5-diaminobenzene and the compounds represented by the above formulas (D-8) to (D-16).

In the synthesis of the polyimide, the diamine represented by the above formula (D-III) may be used in combination with other diamines. Preferred among other diamines are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2- (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - Isopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'- -Aminophenoxy) biphenyl, compounds represented by the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4- , 3,6- (4-aminophenyl) -N, N'-dimethyl-benzidine, a compound represented by the formula (DI) Among the compounds represented by the above formula (D-6), the compounds represented by the above formula (D-7) and the compounds represented by the above formula (D-IV) 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like. When the diamine represented by the above formula (D-III) is used in combination with other diamines, the diamine represented by the formula (D-III) is preferably added in an amount of 0.5% by weight or more, particularly preferably 1% .

The dehydration and cyclization reaction of the polyamic acid for synthesizing the polyimide usable in the present invention can be carried out by a method comprising the steps of (i) heating polyamic acid or (ii) dissolving polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydrating ring- And then heating it as necessary.

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 캜, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered.

On the other hand, in the method of adding the dehydrating agent and dehydrating ring-closing catalyst to the solution of the polyamic acid of the above (ii), for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the amic acid structure. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited thereto. 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 to be 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 of 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 24 hours, more preferably 1 to 10 hours.

The polyimide obtained in the above method (i) can be used as it is for the production of a liquid crystal aligning agent, or after the obtained polyimide is purified, it can be used for the production of a liquid crystal aligning agent. On the other hand, in the method (ii), a reaction solution containing polyimide is obtained. This reaction solution can be used as it is for the preparation of a liquid crystal aligning agent, after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, it can be used for the preparation of a liquid crystal aligning agent or after the polyimide is isolated, Or may be used in 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.

The polyimide which can be used in the present invention may be one in which all of the amic acid structure is dehydrated, or a part of the amic acid structure is dehydrated and cyclized, and the imidization ratio in which the imide ring structure and the amic acid structure coexist is low.

The imidization ratio in the polyimide usable in the present invention is preferably 80% or more, more preferably 85% or more. Here, the "imidization rate" is a percentage of the number of imide rings relative to the sum of the number of amide structures and the number of imide rings in the polymer. At this time, a part of the imide ring may be an isoimide ring. The imidation rate is determined by dissolving polyimide in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference material, . &Lt; / RTI &gt;

[Equation 1]

Imidization rate (%) = (1-A ¹ / A ² × α) × 100

(A ¹ is the peak area derived from the proton of the NH group near 10 ppm of the chemical shift, A ² is the peak area derived from the other protons, and? Is the peak area derived from the polyimide precursor (polyamic acid) The ratio of the number of other proton to one proton of the NH group)

- End Modified Polymers -

The polyamic acid and the polyimide may be of a terminal modified type having a controlled molecular weight. Such a terminal modification type can be synthesized by adding a molecular weight regulator to the reaction system when polyamic acid is synthesized. Examples of the molecular weight regulator include acid monoanhydride, monoamine compound, monoisocyanate compound and the like.

Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride and n-hexadecylsuccinic anhydride. . Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-heptadecylamine, n-octadecylamine, n-octadecylamine, n-octadecylamine, n-hexadecylamine, - eicosylamine, and the like. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The molecular weight modifier is preferably used in an amount of 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and the diamine used in synthesizing the polyamic acid.

- solution viscosity -

The polyamic acid or polyimide thus obtained preferably has a solution viscosity of 20 to 800 mPa 으로 when it is a 10 wt% solution, more preferably a solution viscosity of 30 to 500 mPa 바람직 Do.

The solution viscosity (mPa 占 퐏) of the polymer is a value measured at 25 占 폚 using an E-type rotational viscometer for a polymer solution having a concentration of 10% by weight by using a good solvent for the polymer.

[Other polysiloxane]

As the at least one (other polysiloxane) selected from the group consisting of the polysiloxane having the repeating unit represented by the above formula (S-2), the hydrolyzate thereof and the condensate of the hydrolyzate, X ² in the above formula (S-2) Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

These other polysiloxanes may be prepared by reacting one or more silane compounds (hereinafter also referred to as "raw silane compounds") selected from the group consisting of alkoxysilane compounds and halogenated silane compounds, preferably in an appropriate organic solvent, Or by hydrolysis or hydrolysis and condensation in the presence of a base.

Examples of the raw silane compounds usable herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, Butoxysilane, tetra-tert-butoxysilane, 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 the other polysiloxane include an alcohol compound, a ketone compound, an amide compound or an ester compound or other aprotic compound. 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, 1-butanol, sec-butanol, sec-pentanol, sec-heptanol, heptanol-3, n-hexanol, Octanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, monoalcohol compounds such as sec-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, Butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, ;

Hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4- And? -Diketone compounds such as dione. These ketone compounds may be used alone or in combination of two or more.

Examples of the amide compound include N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, 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, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetoacetate, 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, Glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, 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 polysiloxane is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, and 1 to 1.5 moles per 1 mole of the total amount of the alkoxyl group and the halogen atom contained in the raw material silane compound More preferably, it is molar.

Examples of the catalyst that can be used in the synthesis of other polysiloxanes 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) titanium , Tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di- (Acetylacetonate) titanium, di-sec-butoxy-bis (acetylacetonate) titanium, di-t-butoxy-bis (acetylacetonate) titanium, monoethoxy tris Tris (acetylacetonate) titanium, mono-i-propoxy tris (acetyl (Acetyl acetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium (Ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethylacetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis Titanium, di-sec-butoxy-bis (ethyl acetoacetate Mono-n-propoxy tris (ethylacetoacetate) titanium, di-t-butoxy-bis (ethyl acetoacetate) titanium, monoethoxy tris Propoxy tris (ethylacetoacetate) titanium, mono-n-butoxy tris (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) mono (acetylacetonate) titanium, bis (Ethyl acetoacetate) titanium;

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

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, monomethyldiethanol Amine, triethanolamine, diazabicyclooctane, diazabicyclo-nonane, 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.

The water added during the synthesis of the other polysiloxane may 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 polysiloxane 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.

[Content ratio of other polymer]

When the liquid crystal aligning agent of the present invention contains other polymers together with the above-described Shinan acid-containing polysiloxane of the present invention, 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 and a polyamic acid and a polyimide, the more preferable ratio of the two is that the 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 a radiation-sensitive polyorganosiloxane and other polysiloxane, the more preferable ratio of the two is that the amount of other polysiloxane relative to 100 parts by weight of the synnosane- 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, or other polysiloxane desirable.

<Curing agent, curing catalyst and curing accelerator>

The curing agent and the curing catalyst may be contained in the liquid crystal aligning agent of the present invention for the purpose of strengthening the cross-linking reaction of the radiation-sensitive polyorganosiloxane. The curing accelerator is used for the purpose of promoting the curing reaction May be contained in the liquid crystal aligning agent of the present invention.

As the curing agent, a curing agent generally used for curing a curing composition containing an epoxy group or a compound having an epoxy group can be used. Examples of the curing agent include a polyvalent amine, a polycarboxylic acid anhydride, and a polycarboxylic acid can do.

Examples of the polycarboxylic acid anhydrides include anhydrides of cyclohexanetricarboxylic acid and other polycarboxylic acid anhydrides.

Specific examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid- 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride, and the like. Examples of other polycarboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methyl In addition to the tetracarboxylic acid dianhydride generally used for the synthesis of the compound represented by the following general formula (5) and the polyamic acid, α, α, β, α, Aldehyde reaction products of alicyclic compounds having a conjugated double bond such as terpinene and alo cymene with maleic anhydride, hydrogenated products thereof, and the like.

(In the formula (5), r is an integer of 1 to 20)

As the curing catalyst, for example, antimony hexafluoride compound, hexafluorophosphate compound, aluminum trisacetylacetonate and the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

As the curing accelerator, for example, an imidazole compound;

A quaternary compound;

Quaternary amine compounds;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetyl acetone complex;

Boron compounds such as boron trifluoride, triphenyl borate; Metal halide compounds such as zinc chloride, zinc stannate,

High melting point dispersing latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amines and epoxy resins;

A microcapsulated latent curing accelerator in which the surface of a quaternary phosphonium salt or the like is coated with a polymer;

Amine salt type latent curing accelerator;

High-temperature dissociation type thermal cationic polymerization latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

<Epoxy Compound>

The epoxy compound can be used from the viewpoint of improving adhesion to the substrate surface of the liquid crystal alignment layer formed from the liquid crystal aligning agent of the present invention.

As the epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Aminomethylcyclohexane and the like can be preferably used. The proportion of these epoxy compounds to be used is preferably 40 parts by weight or less, more preferably 0.1 parts by weight or less, and more preferably 0.1 parts by weight or less, based on 100 parts by weight of the sum of the polymers (total of the radiation-sensitive polyorganosiloxane and other polymer, To 30 parts by weight.

<Functional silane compound>

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

The use ratio of these functional silane compounds is preferably 4 parts by weight or less based on 100 parts by weight of the total of the polymers.

<Surfactant>

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 total amount of the liquid crystal aligning agent.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains, as described above, a radiation-sensitive polyorganosiloxane as an essential component and, in addition, other components as necessary, but preferably a solution in which each component is dissolved in an organic solvent Is prepared as a phase composition.

As the organic solvent which can be used for producing 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 for the liquid crystal aligning agent of the present invention is optionally different depending on the kind of the other polymer to be added.

When 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, preferable organic solvents are those used for the synthesis reaction of polyamic acid Illustrative solvents are: Here, the poor solvents exemplified as those that can be used in the synthesis reaction of the polyamic acid can also be suitably selected and used in combination.

Particularly preferred organic solvents that can be used in this case include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene Propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl pro O can be cited carbonate, isoamyl isobutyrate, di-isopentyl ether. These may be used alone or in combination of two or more.

On the other hand, as the preferred organic solvent in the case where the liquid crystal aligning agent of the present invention contains only the radiation-sensitive polyorganosiloxane as the polymer or contains the radiation-sensitive polyorganosiloxane and the other polysiloxane, Ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Ethylene glycol, methyl cellosolve acetate , Ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, Butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, 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 solid concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of the 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, and the like. The preferred solid concentration ranges from 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is coated on the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, 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, When the concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, so that 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 deteriorated.

The particularly preferable range of the solid concentration is different depending on the method used when applying the liquid crystal aligning agent 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 at which the liquid crystal aligning agent of the present invention is produced is preferably 0 to 200 캜, more preferably 20 to 60 캜.

&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 a liquid crystal alignment film, for example, there can be mentioned a method in which a liquid crystal alignment film of the present invention is coated on a substrate to form a coating film, and then the liquid crystal alignability is imparted to the above film by 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 占 퐉, more preferably 0.005 to 0.5 占 퐉, as the thickness after removing the solvent.

Examples of the substrate include transparent substrates including plastics such as glass such as float glass and soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) Can be used.

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 photo-etching method, a method of using a mask to form a transparent conductive film, or the like is used.

Subsequently, the coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation, and if necessary, further subjected to heat treatment at a temperature of 150 to 250 ° C, preferably for 1 to 120 minutes, Thereby forming a liquid crystal alignment film. Here, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm, for example, can be used as the radiation, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable, and 300 nm to 365 nm And ultraviolet rays including light having a wavelength of &lt; RTI ID = 0.0 &gt; Since the liquid crystal aligning agent of the present invention does not cause a photoreaction by light in a long wavelength region of 365 nm or more in wavelength, it is possible to manufacture a liquid crystal panel without a process problem, and the long- . &Lt; / RTI &gt;

When the radiation is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction to give a pre-tilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined.

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, when the liquid crystal aligning agent of the present invention is used, excellent liquid crystal alignability can be imparted even when the dose of radiation in the photo alignment method is 3,000 J / m 2 or less, more preferably 1,000 J / m 2 or less, particularly 800 J / Which is effective in reducing the manufacturing cost of the liquid crystal display element.

<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.

One pair (two pieces) of substrates each having a liquid crystal alignment film formed thereon as described above are prepared, the liquid crystal alignment film of the liquid crystal alignment film is confronted so that the polarization direction of the irradiated linearly polarized radiation is at a predetermined angle, , A 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 using the liquid crystal cell to a temperature at which the isotropic phase takes place, and then cool to room temperature to remove the flow orientation at the time of injection.

The polarizing plate may be 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.

In the case where the liquid crystal alignment film is horizontally oriented, the angle formed by the polarization direction of linearly polarized light irradiated and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed, thereby obtaining a TN type or STN type liquid crystal cell A liquid crystal display element can be obtained.

On the other hand, when the liquid crystal alignment film is vertically aligned, the cell is constructed such that the easy axis of alignment in two substrates on which the liquid crystal alignment film is formed is parallel, and the polarizing plate is polarized at an angle So that a liquid crystal display element having a vertically aligned 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 for forming a nematic liquid crystal are preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane 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. Further, it is also possible to add a cholesteric liquid crystal such as cholestyl chloride, cholesteryl nonanoate or cholesteryl carbonate to the liquid crystal; Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck); and a ferroelectric liquid crystal such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate may be further added.

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, Clock liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, and the like.

Examples of the polarizing plate used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film " 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 H film itself .

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

[Example]

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

In the following examples, the weight average molecular weight is a polystyrene reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68 kgf / ㎠

The epoxy equivalent was measured in accordance with JIS C2105 "hydrochloric acid-methyl ethyl ketone method ".

The following synthesis examples were repeated with the following synthesis scales as necessary to obtain the required amount of product to be used in the following synthesis examples and examples.

&Lt; Synthesis of polyorganosiloxane having epoxy group >

Synthesis Example 1

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, , And mixed at room temperature. Subsequently, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane EPS-1 having an epoxy group Was obtained as a viscous transparent liquid.

¹ H-NMR analysis of this polyorganosiloxane EPS-1 revealed that a peak based on the epoxy group was obtained at a theoretical intensity in the vicinity of chemical shift (?) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction .

The viscosity, Mw and epoxy equivalent of the polyorganosiloxane EPS-1 are shown in Table 1.

Synthesis Examples 2 and 3

Polyorganosiloxanes EPS-2 and 3 having an epoxy group were obtained as viscous transparent liquids in the same manner as in Synthesis Example 1, except that the starting materials were as shown in Table 1.

Mw and epoxy equivalent of these polyorganosiloxanes are shown in Table 1.

Synthesis Example 4

150 g of isopropanol, 5.4 g of a 10 wt% aqueous solution of tetramethylammonium hydroxide (containing 5.93 mmol of tetramethylammonium hydroxide and 270 mmol of water) and 12 g of water were charged into a reaction vessel equipped with a stirrer and a thermometer, 42.5 g (180 mmol) of glycidoxypropyltrimethoxysilane was slowly added thereto, and the reaction was continued by stirring at room temperature for 20 hours.

After completion of the reaction, 200 g of toluene was added to the reaction mixture, and isopropanol was removed under reduced pressure. For the residues, the reaction solution was washed with distilled water using a separatory funnel. After washing with distilled water repeatedly until the aqueous layer of the separatory funnel became neutral, the organic layer was separated, dehydrated with a sodium sulfate anhydride, and then toluene was distilled off under reduced pressure to obtain an epoxy group-containing polyorganosiloxane EPS-4 .

The weight average molecular weight Mw and the epoxy equivalent of the polyorganosiloxane EPS-4 are shown in Table 1.

The abbreviations of the raw material silane compounds in Table 1 are as follows.

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

GPTMS: 3-glycidyloxypropyltrimethoxysilane

&Lt; Synthesis of cinnamic acid derivative (1) >

[Synthesis of the compound represented by the above formula (2-1)] [

Synthesis Example 2-1 (1)

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

12 g of decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were added to a 200 mL branched flask equipped with a reflux tube, and the reaction was carried out under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, purified with a silica column, and recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain the compound (2- (Purity 98.0%) of the title compound (1-1-1). The compound thus obtained is hereinafter referred to as "compound (2-1-1-1 (1))".

Synthesis Example 2-1 (2)

Compound (2-1-1-1) was synthesized by a method other than Synthesis Example 2-1 (1) according to the following reaction formula.

72 g of decylsuccinic anhydride, 49 g of 4-aminocinnamic acid, 70 mL of triethylamine, 500 mL of toluene and 200 mL of tetrahydrofuran were fed into a 1 L eggplant flask equipped with a reflux tube, a nitrogen inlet tube and a Dean Stark tube And the reaction was carried out under reflux for 36 hours. After completion of the reaction, the reaction mixture was washed sequentially with diluted hydrochloric acid and water, and then the organic layer was dried with magnesium sulfate, concentrated, and recrystallized from a mixed solvent containing ethanol and tetrahydrofuran to obtain Compound (2-1 -1-1) as white crystals (purity 99%). The compound thus obtained is hereinafter referred to as "compound (2-1-1-1 (2))".

Synthesis Example 2-1 (3)

Compound (2-1-1-1) was synthesized by a method different from Synthesis Examples 2-1 (1) and 2-1 (2) according to the following reaction formula.

(Synthesis of compound (2-1-1-1A)

24 g of decylsuccinic anhydride, 22 g of 4-iodoaniline and 200 mL of acetic acid were added to a 500 mL branched flask equipped with a reflux tube, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over magnesium sulfate, concentrated, dried and recrystallized with ethanol to obtain 33 g of a compound (2-1-1-1A) .

(Synthesis of compound (2-1-1-1)) [

26.4 g of the compound (2-1-1-1A) obtained above and 1.38 g of tetrakistriphenylphosphine palladium were introduced into a 1 L three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, and the flask was purged with nitrogen. To this was added 4.8 mL of dried and deaerated acrylic acid, 25 mL of triethylamine and 600 mL of N, N-dimethylformamide with a syringe, and the reaction was carried out at 90 DEG C for 3 hours with stirring.

After completion of the reaction, the reaction mixture was poured into an ice-cooled aqueous solution of dilute hydrochloric acid, and ethyl acetate was added to separate the layers. The organic layer was washed successively with dilute hydrochloric acid, aqueous sodium thiosulfate solution and water, dried with magnesium sulfate, purified with a silica column, and recrystallized from a mixed solvent containing ethanol and tetrahydrofuran to obtain the compound (2-1-1 -1) as white crystals (purity 98.0%). The compound thus obtained is hereinafter referred to as "compound (2-1-1-1 (3))".

Synthesis Example 2-1 (4)

(2-1) represented by the following formula was obtained by carrying out the same processes as in Synthesis Example 2-1 (1) except that 18 g of octadecylsuccinic anhydride was used instead of decylsuccinic anhydride in Synthesis Example 2-1 (1) -1-2) as white crystals (purity 98.5%).

[Synthesis of the compound represented by the above formula (2-2)

Synthesis Example 2-2 (1)

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

(Synthesis of compound (2-2-1-1A)

30 g of cyclohexane-1,2,4-tricarboxylic anhydride, 33 g of 4-iodoaniline and 200 mL of acetic acid were added to a 500 mL eggplant-shaped flask equipped with a reflux tube, and the reaction was carried out under reflux for 2 hours . After completion of the reaction, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water, dried over magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 31 g of a gray crystal of the compound (2-2-1-1A).

(Synthesis of compound (2-2-1-1B)

15 g of the compound (2-2-1-1A) obtained above, 20 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were introduced into a 100 mL eggplant-shaped flask equipped with a reflux condenser and a nitrogen inlet tube , And the reaction was carried out at 80 DEG C for 1 hour. After completion of the reaction, thionyl chloride was removed under reduced pressure, methylene chloride was added to the residue, and the organic layer was washed sequentially with water and a saturated aqueous solution of sodium hydrogencarbonate. Subsequently, the organic layer was dried over magnesium sulfate, and methylene chloride was removed under reduced pressure, and 80 mL of tetrahydrofuran was added.

Apart from this, 6.8 g of 4,4,5,5,5-pentafluoropentanol, 6.5 mL of pyridine and 20 mL of tetrahydrofuran were added to a 200 mL three-necked flask equipped with a dropping funnel, thermometer and nitrogen inlet tube And ice-cooled. A tetrahydrofuran solution containing a reaction product of the compound (2-2-1-1A) and thionyl chloride was added dropwise thereto, and the reaction was carried out with stirring for 3 hours under ice-cooling. After completion of the reaction, the reaction mixture was washed sequentially with ethyl acetate, dilute hydrochloric acid and water. The organic layer was dried with magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 14 g of a gray crystal of the compound (2-2-1-1B).

(Synthesis of compound (2-2-1-1)) [

In a 500 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 14 g of the compound (2-2-1-1B) obtained above, 1.8 mL of acrylic acid, 11 mL of triethylamine, 0.46 g of tetrakistriphenylphosphine palladium and After 250 mL of N, N-dimethylformamide was added and degassed, the reaction was carried out at 90 占 폚 for 3 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and washed sequentially with diluted hydrochloric acid and water. The organic layer was purified with a silica column, concentrated, and recrystallized from methanol to obtain 9.0 g of a white crystal of the compound (2-2-1-1) with a purity of 98%.

Synthesis Example 2-2 (2)

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

(Synthesis of compound (2-2-1-2A)

12 g of cyclohexane-1,2,4-tricarboxylic anhydride, 30 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were fed to a 200 mL eggplant type flask equipped with a reflux tube, The reaction was carried out under reflux for 1 hour. After completion of the reaction, thionyl chloride was removed under reduced pressure, and methylene chloride was added to the residue. The organic layer was washed sequentially with a saturated aqueous sodium hydrogencarbonate solution and water, dried with magnesium sulfate, concentrated and dried. Hydrofluorene was added to form a solution.

On the other hand, 19 g of? -Cholestanol, 8.0 mL of pyridine and 100 mL of toluene were introduced into a 300 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen inlet tube and cooled with an ice bath. A tetrahydrofuran solution containing the reaction product of cyclohexane-1,2,4-tricarboxylic anhydride and thionyl chloride as described above was slowly added dropwise, and the reaction was carried out at room temperature for 4 hours with stirring. After completion of the reaction, extraction was carried out with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and then recrystallized from a mixed solvent containing ethyl acetate and hexane to obtain 18 g of a compound (2-2-1-2A).

(Synthesis of compound (2-2-1-2)

11 g of the compound (2-2-1-2A) obtained above, 3.3 g of 4-aminocinnamic acid, 0.1 mL of triethylamine and 100 mL of toluene were placed in a 200 mL eggplant-shaped flask equipped with a Dean Stark tube, The reaction was carried out at reflux for a period of time. After completion of the reaction, the reaction mixture was washed with water. The organic layer was dried over magnesium sulfate and then recrystallized from a mixed solvent containing ethyl acetate and tetrahydrofuran to obtain 6.1 g of white crystals (purity: 99.2%) of the compound (2-2-1-2).

[Synthesis of a compound represented by the above formula (3-2)] [

Synthesis Example 3-2 (1)

Compound (3-2-1-1) was synthesized according to the following reaction formula.

(Synthesis of compound (3-2-1-1A)

A 300-mL three-necked flask equipped with a thermometer and a nitrogen inlet tube was charged with 9.7 g of 4-nitrocinnamic acid, 12 g of 4,4,4-trifluoro-1-iodobutane, 14 g of potassium carbonate, -Pyrrolidone was added, and the reaction was carried out by stirring at 50 DEG C for 1 hour. After completion of the reaction, ethyl acetate was added to the reaction mixture for extraction. The extract was washed with water, dried over magnesium sulfate, concentrated, and dried to obtain 14 g of a compound (3-2-1-1A).

(Synthesis of compound (3-2-1-1B)

14 g of the compound (3-2-1-1A) obtained above, 53 g of tin chloride dihydrate and 150 mL of ethanol were charged into a 300 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, and the mixture was stirred at 70 DEG C for 1 hour The reaction was carried out with stirring. After completion of the reaction, the reaction mixture was poured into ice water, neutralized with 2 M aqueous sodium hydroxide solution, ethyl acetate was added, and the precipitate was removed. Ethyl acetate was added to the filtrate for extraction. The extract was washed with water, dried over magnesium sulfate, concentrated, and dried to obtain 12 g of a compound (3-2-1-1B).

(Synthesis of compound (3-2-1-1)) [

12 g of the compound (3-2-1-1B) obtained above, 8.7 g of 1,2,4-cyclohexanetricarboxylic acid anhydride and 100 mL of acetic acid were charged into a 200 mL branched flask equipped with a reflux condenser and a nitrogen inlet tube And the reaction was carried out under reflux for 1 hour. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was washed with water and dried with magnesium sulfate, followed by concentration, drying, and recrystallization from a mixed solvent containing ethyl acetate and hexane to obtain a white crystal (purity: 98.3%) of the compound (3-2-1-1) 11 g.

&Lt; Synthesis of other polymer >

[Synthesis of polyamic acid]

Synthesis Example PA-1

As the tetracarboxylic acid dianhydride, 109 g (0.50 molar equivalent) of pyromellitic dianhydride and 98 g (0.50 molar equivalent) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4- 200 g (1.0 molar equivalent) of diaminodiphenyl ether was dissolved in 2,290 g of N-methyl-2-pyrrolidone and reacted at 40 DEG C for 3 hours. Then, 1,350 g of N-methyl- To obtain about 4,000 g of a solution containing 10 wt% of polyamic acid (PA-1). The solution viscosity of this polyamic acid solution was 210 mPa s.

Synthesis Example PA-2

98 g (0.50 molar equivalent) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 109 g (0.50 molar equivalent) of pyromellitic dianhydride as the tetracarboxylic dianhydride, 4,4 ' (1.0 molar equivalent) of diaminodiphenylmethane was dissolved in 2,290 g of N-methyl-2-pyrrolidone and reacted at 40 DEG C for 3 hours. Then, 1,350 g of N-methyl-2-pyrrolidone To obtain about 4,000 g of a solution containing 10% by weight of polyamic acid (PA-2). The solution viscosity of this polyamic acid solution was 135 mPa..

Synthesis Example PA-3

196 g (1.0 molar equivalent) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200 g (1.0 molar equivalent) of 4,4'-diaminodiphenyl ether as a diamine were added, (PA-3) was dissolved in 2, 246 g of N-methyl-2-pyrrolidone and reacted at 40 DEG C for 4 hours, followed by addition of 1,321 g of N-methyl- % &Lt; / RTI &gt; The solution viscosity of this polyamic acid solution was 220 mPa..

Synthesis Example PA-4

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

Synthesis Example PA-5

224 g (1.0 molar equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 molar equivalent) of 4,4'-diaminodiphenyl ether as diamine were dissolved in N- Methyl-2-pyrrolidone and reacted at 40 DEG C for 4 hours to obtain about 2,800 g of a solution containing 15 wt% of polyamic acid (PA-5).

The solution viscosity of the polyamic acid solution measured as a solution having a polymer concentration of 10 wt% by adding a small amount of the solution and adding N-methyl-2-pyrrolidone was 190 mPa..

[Synthesis of polyimide]

Synthesis Example PI-1

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- 157 g (0.50 mol) of p-phenylenediamine as diamine and 95 g (0.88 mol) of p-phenylenediamine as diamine 32 g (0.10 mol) of 2,2-ditrifluoromethyl-4,4-diaminobiphenyl, 6.4 g (0.010 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, 4.0 g (0.015 mol) of decanoxy-2,5-diaminobenzene was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 9 hours. A small amount of the obtained polyamic acid solution was fractionated and the solution viscosity was measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone to obtain 58 mPa.s.

2,740 g of N-methyl-2-pyrrolidone, 396 g of pyridine and 409 g of acetic anhydride were added to the obtained polyamic acid solution, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration ring-closure reaction were removed from the system by this operation, About 2,500 g of a solution containing 15% by weight of polyimide (PI-1) at a rate of about 95% was obtained.

A small amount of the polyimide solution was collected, the solvent was removed under reduced pressure, and the solution viscosity was measured as a solution having a polymer concentration of 8.0 wt% by dissolving in? -Butyrolactone was 33 mPa 占 퐏.

Synthesis Example PI-2

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 1,3-dihydroxy-8-methyl-5- 157 g (0.50 mol) of p-phenylenediamine (0.89 mol) as diamine, (0.10 mole) of bisaminopropyltetramethyldisiloxane and 13 g (0.020 mole) of 3,6-bis (4-aminobenzoyloxy) cholestane, 8.1 g (0.030 mole) of N-octadecylamine as monoamine, Was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours. A small amount of the obtained polyamic acid solution was fractionated and the solution viscosity was measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa.s.

Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added, followed by dehydration ring-closure reaction at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 2,400 g of a solution containing 15% by weight of polyimide (PI-2) having an imidization rate of about 95% .

A small amount of this polyimide solution was collected and the solution viscosity was measured as a solution having a polymer concentration of 6.0% by weight by adding N-methyl-2-pyrrolidone to obtain a solution viscosity of 18 mPa.s.

Synthesis Example PI-3

224 g (1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 107 g (0.99 mole) of p-phenylenediamine as diamine and 3,6-bis 6.000 g (0.010 mol) of benzoyloxy) cholestane was dissolved in 3,039 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours to obtain a solution containing 10 wt% of polyamic acid. The solution viscosity of this polyamic acid was 260 mPa..

Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 396 g of pyridine and 306 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 3,500 g of a solution containing 9.0% by weight of polyimide (PI-3) having an imidization rate of about 89% .

A small amount of this polyimide solution was collected and the solution viscosity was measured as a solution having a polymer concentration of 5.0% by weight by adding N-methyl-2-pyrrolidone was 74 mPa.s.

Synthesis Example PI-4

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 13 g (0.50 mol) of 1,3,3a, 4,5,9b-hexahydro-8- 157 g (0.50 mol) of p-phenylenediamine 89 g (0.82 mol) of p-phenylenediamine as diamine ), 32 g (0.10 mol) of 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 0.1 g of 1- (3,5-diaminobenzoyloxy) -4- 25 g (0.059 mol) of methylbenzoyloxy) -cyclohexane and 4.0 g (0.011 mol) of octadecanoxy-2,5-diaminobenzene were dissolved in 2,175 g of N-methyl-2-pyrrolidone, And reacted for 6 hours to obtain a solution containing polyamic acid. The solution viscosity of the obtained polyamic acid solution was measured as a solution having a polymer concentration of 10% by weight by adding a small amount of the solution and adding N-methyl-2-pyrrolidone to obtain 110 mPa 占 퐏.

To 1,500 g of the obtained polyamic acid solution, 3,000 g of N-methyl-2-pyrrolidone was added, and 221 g of pyridine and 228 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 4,000 g of a solution containing 10% by weight of polyimide (PI-4) having an imidization rate of about 92% .

A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polymer concentration of 4.5 wt% by adding N-methyl-2-pyrrolidone was 28 mPa..

Synthesis Example PI-5

19.9 g (0.089 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as a tetracarboxylic dianhydride, 6.8 g (0.063 mol) of p-phenylenediamine as a diamine, 4,4'-diaminodiphenyl 3.6 g (0.018 mol) of methane and 4.7 g (0.009 mol) of the compound represented by the above formula (D-10) were dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours. A small amount of the obtained polyamic acid solution was fractionated and the solution viscosity was measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 115 mPa.s.

Subsequently, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 14 g of pyridine and 18 g of acetic anhydride were added and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 220 g of a solution containing 15.4 wt% of polyimide (PI-5) having an imidization rate of about 77% .

A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 84 mPa.s.

Synthesis Example PI-6

20.9 g (0.093 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic acid dianhydride, 9.2 g (0.085 mole) of p-phenylenediamine as a diamine, Was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polymer concentration of 10% by weight, and found to be 126 mPa.s.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 7.4 g of pyridine and 9.5 g of acetic anhydride were added, followed by dehydration ring closure at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 220 g of a solution containing 16.1 wt% of polyimide (PI-6) having an imidization rate of about 54% .

A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 75 mPa.s.

Synthesis Example PI-7

18.8 g (0.084 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 7.4 g (0.068 mol) of p-phenylenediamine as a diamine, Was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polymer concentration of 10% by weight, and found to be 126 mPa.s.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 6.6 g of pyridine and 8.5 g of acetic anhydride were added, followed by dehydration ring closure at 110 占 폚 for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 210 g of a solution containing 15.9% by weight of polyimide (PI-7) having an imidization rate of about 55% .

A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 75 mPa.s.

Synthesis Example PI-8

19.1 g (0.085 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic acid dianhydride, 7.4 g (0.069 mol) of p-phenylenediamine as a diamine, Was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polymer concentration of 10% by weight, and found to be 206 mPa.s.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 6.7 g of pyridine and 8.7 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 200 g of a solution containing 15.8 wt% polyimide (PI-8) having an imidization rate of about 52% .

A small amount of this polyimide solution was collected, and the solution viscosity measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 105 mPa..

Synthesis Example PI-9

17.3 g (0.077 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, 5.9 g (0.054 mol) of p-phenylenediamine as a diamine, 4.1 g (0.008 mol) of the compound to be displayed and 7.7 g (0.016 mol) of the compound represented by the above formula (D-8) were dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 4 hours . A small amount of the obtained polyamic acid solution was collected and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polymer concentration of 10% by weight, and found to be 117 mPa 占 퐏.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, followed by dehydration ring closure at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone to obtain about 210 g of a solution containing 15.4% by weight of polyimide (PI-9) having an imidization rate of about 55% .

A small amount of this polyimide solution was collected, and the solution viscosity was measured as a solution having a polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone to obtain a solution viscosity of 109 mPa.s.

[Synthesis of other polysiloxane]

Synthesis Example PS-1

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. A maleic anhydride aqueous solution obtained by dissolving 0.26 g of maleic anhydride in 10.8 g of water, prepared in a separate flask with a capacity of 20 mL, was added and heated at 60 캜 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% by weight of the polyorganosiloxane PS-1. The weight average molecular weight Mw of PS-1 was 5,100.

<Synthesis of radiation-sensitive polyorganosiloxane>

Example IE-1

5.0 g of the polyorganosiloxane EPS-1 having the epoxy group obtained in Synthesis Example 1 and 5.0 g of the compound obtained in Example 2-1 (1) as the cinnamic acid derivative (1) were placed in a 200 mL three- 5.18 g (corresponding to 50 mol% with respect to the epoxy group of the polyorganosiloxane) and 0.5 g of tetrabutylammonium bromide were fed into a flask equipped with a stirrer, N-dimethylacetamide was added, and the reaction was carried out at 120 DEG C for 10 hours. After completion of the reaction, methanol was added to form a precipitate. The resulting solution was dissolved in ethyl acetate, and the resulting solution was washed three times with water. The solvent was distilled off to obtain a radiation-sensitive polyorganosiloxane S-IE- 7.8 g of a powder was obtained. The weight average molecular weight Mw of the radiation-sensitive polyorganosiloxane S-IE-1 was 18,100.

Examples IE-2 to 8

In the same manner as in Example IE-1 except that the kind of the polyorganosiloxane having an epoxy group and the kind and amount of the cinnamic acid derivative (1) were changed as shown in Table 2, respectively, in the above Example IE-1 Sensitive radiation-sensitive polyorganosiloxanes S-IE-2 to S-IE-8 were synthesized, respectively. The weight average molecular weights Mw of these radiation-sensitive polyorganosiloxanes are shown in Table 2.

In Examples IE-6 and 7, two kinds of cinnamic acid derivatives (1) were used.

The "amount of use" of the cinnamic acid derivative (1) in Table 2 means the ratio of the polyorganosiloxane having an epoxy group to the silicon atom.

&Lt; Production of liquid crystal aligning agent and evaluation of storage stability >

Example IE-9

100 parts by weight of the radiation-sensitive polyorganosiloxane S-IE-1 obtained in the above Example IE-1 and the solution containing the polyamic acid PA-1 obtained in Synthesis Example PA-1 as another polymer were dissolved in PA-1 Methyl-2-pyrrolidone and butyl cellosolve were added thereto to prepare a solution having a solvent composition of 1-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), and a solid content concentration of 3.0% by weight. This solution was filtered with a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent A-IE-1.

The liquid crystal aligning agent A-IE-1 was stored at -15 캜 for 6 months. Viscosity measured by an E-type viscometer at 25 ° C before and after storage was measured. The storage stability of the liquid crystal aligning agent A-IE-1 was evaluated as " good "when the change rate of the solution viscosity before and after storage was 10% or less and the storage stability was " good "

Examples IE-10 to 32

In the same manner as in Example IE-9 except that the kind of the radiation-sensitive polyorganosiloxane and the kind and amount of the other polymer were changed as shown in Table 3 in the above Example IE-9, liquid crystal aligning agent A -IE-2 to A-IE-24, respectively. Table 3 shows the results of evaluating the storage stability of each liquid crystal aligning agent as measured in the same manner as in Example IE-9.

Examples IE-33 to 36

In the same manner as in Example IE-9 except that the kind and amount of the other polymer were changed as shown in Table 3 and the epoxy compound of the kind and amount described in Table 3 was used in the above Example IE-9, Was prepared and filtered with a filter having a pore size of 1 占 퐉 to prepare liquid crystal aligning agents A-IE-25 to A-IE-28, respectively.

In Table 3, the epoxy compounds E-1 and E-2 each represent a compound represented by the following formula (E-1) or (E-2).

Example IE-37

The other polysiloxane PS-1-containing solution obtained in Synthesis Example PS-1 as the other polymer was converted into PS-1 in an amount corresponding to 500 parts by weight, and the amount of the polysiloxane PS-1 obtained in Synthesis Example PS- 100 parts by weight of polyorganosiloxane S-IE-1 was added, and 1-ethoxy-2-propanol was further added to obtain a solution having a solid concentration of 4.0% by weight. This solution was filtered with a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent A-IE-29.

The evaluation results of the storage stability of this liquid crystal aligning agent A-IE-29, which were examined in the same manner as in the above-mentioned Example IE-9, are shown in Table 3.

Example IE-38

&Lt; Production of vertical alignment type liquid crystal display device >

The liquid crystal aligning agent A-IE-1 prepared in the above Example IE-9 was coated on the transparent electrode surface of the glass substrate with a transparent electrode containing ITO film using a spinner and prebaked for 1 minute on a hot plate at 80 캜 , The inside of the system was heated at 200 ° C for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 μm. Subsequently, an Hg-Xe lamp and a Glane Taylor prism were used on the surface of the coating film to irradiate a polarizing ultraviolet ray containing 313 nm of a bright line of 1,000 J / m 2 from a direction perpendicular to the substrate from 40 ° to form a liquid crystal alignment film. The same operation was repeated to prepare one pair (two pieces) of substrates having a liquid crystal alignment film.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer periphery of one of the substrates having the liquid crystal alignment film by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The optical axis was compressed so that the projection direction with respect to the substrate surface was inverted, 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 at 150 占 폚 for 10 minutes and gradually cooled to room temperature. Subsequently, a polarizing plate was vertically aligned on both outer sides of the substrate, and the vertically aligned liquid crystal display device was manufactured by joining the polarizing plates so that the polarizing directions thereof were orthogonal to each other and at an angle of 45 degrees with respect to the projection direction of the ultraviolet optical axis of the liquid crystal alignment film.

These liquid crystal display elements were evaluated by the following methods. The evaluation results are shown in Table 4.

&Lt; Evaluation of liquid crystal display element &

(1) Evaluation of liquid crystal alignment property

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

(2) Evaluation of Pretilt Angle

With respect to the liquid crystal display device manufactured as described above, 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) Evaluation of 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. The voltage remaining in the liquid crystal cell immediately after the DC voltage was cut off, The residual DC voltage was determined by the erase method.

Examples IE-39 to 64

In the same manner as in Example IE-38 except that the liquid crystal aligning agent described in Table 4 was used in the above Example IE-38, vertical alignment type liquid crystal display devices were produced and evaluated respectively. The evaluation results are shown in Table 4.

Example IE-65

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

The liquid crystal aligning agent A-IE-21 prepared in the above Example IE-29 was coated on the transparent electrode surface of the glass substrate with a transparent electrode including the ITO film using a spinner and heated at 180 캜 for 1 hour to obtain a film thickness of 0.1 Mu m. Using a Hg-Xe lamp and a gantry prism on the surface of this coating film, 1,000J / m &lt; 2 &gt; of polarized ultraviolet rays including a 313 nm bright line was irradiated from the direction normal to the substrate from 40 deg. .

The same operation as above 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 aluminum oxide spheres 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 superposed so that the polarizing ultraviolet ray irradiation directions were orthogonal And heated at 150 ° C for 1 hour to thermally cure the adhesive. 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 gradually cooled to room temperature. Subsequently, a TN alignment type liquid crystal display device was manufactured by joining the polarizing plates on both outer sides of the substrate so that their polarization directions were perpendicular to each other and parallel to the polarization direction of the liquid crystal alignment film.

The liquid crystal alignment properties, the voltage holding ratio and the baking of the liquid crystal display were evaluated in the same manner as in Example IE-38. The evaluation results are shown in Table 4.

Example IE-66

In the same manner as in Example IE-65 except that the liquid crystal aligning agent A-IE-24 prepared in Example IE-32 was used as the liquid crystal aligning agent in the above Example IE-65, the TN alignment type liquid crystal display device was manufactured And evaluated. The evaluation results are shown in Table 4.

&Lt; Evaluation of Physical Properties of Coating Film &

Examples IE-67 to 93

(1) Evaluation of i-ray absorption

The liquid crystal aligning agents described in Table 5 were each spin coated on a quartz substrate, prebaked on a hot plate at 80 DEG C for 1 minute, and then heated at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. The UV absorption spectrum of the substrate having this coating film was measured in a wavelength range of 250 to 500 nm using a spectrophotometer (manufactured by Hitachi, Ltd., type "U-2010").

The absorbance at 365 nm was evaluated as "good" when the maximum absorbance in this wavelength range was 100, and " poor "

The evaluation results are shown in Table 5.

(2) Evaluation of heat resistance

In the same manner as in Example IE-28 except that the liquid crystal aligning agent described in Table 5 was used and the post-baking temperature was set to 250 캜 in the <Production of Vertically Aligned Liquid Crystal Display Device> of Example IE-38 The vertical alignment type liquid crystal display device was manufactured. The resulting liquid crystal display element was evaluated as "good" with good vertical alignment (showing a uniform black display), and "defective" when light leakage was observed.

The evaluation results are shown in Table 5.

Examples IE-94 and 95

(1) Evaluation of i-ray absorption

UV absorption spectra in the wavelength range of 250 to 500 nm were measured in the same manner as in Examples IE-67 to 93 except that the liquid crystal aligning agent described in Table 5 was used. The evaluation results are shown in Table 5.

(2) Evaluation of heat resistance

In Example IE-65, except that the liquid crystal aligning agent described in Table 5 was used and the post-baking temperature was set to 250 DEG C in the <TN alignment type liquid crystal display device of Example IE-65> A TN alignment type liquid crystal display device was produced. The resulting liquid crystal display element was evaluated as "good" with good vertical alignment (showing a uniform black display), and "defective" when light leakage was observed.

The evaluation results are shown in Table 5.

Comparative Example IE-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 very large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 67 g of polyamic acid.

&Lt; Preparation of liquid crystal aligning agent &

The polyamic acid synthesized above was dissolved in a mixed solvent (mixing ratio = 50: 50 (weight ratio)) containing N-methyl-2-pyrrolidone and butyl cellosolve to prepare a solution having a solid concentration of 3.0 wt%. This solution was filtered with a filter having an opening diameter of 1 탆 to prepare a liquid crystal aligning agent RA-IE-1.

&Lt; Evaluation of Physical Properties of Coating Film &

Properties of coating films were evaluated in the same manner as in Examples IE-67 to 93 except that the above-prepared liquid crystal aligning agent RA-IE-1 was used.

The evaluation results are shown in Table 5.

&Lt; Production of liquid crystal aligning agent and evaluation of storage stability >

Examples IE-96 to 107

In the same manner as in Example IE-16 except that the kind of the radiation-sensitive polyorganosiloxane and the kind and the amount of the other polymer were changed as shown in Table 6, the liquid crystal aligning agent A- IE-30 to A-IE-41 were respectively prepared. Table 6 shows the results of evaluating the storage stability of each liquid crystal aligning agent in the same manner as in Example IE-16.

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

Examples IE-108-119

In the same manner as in Example IE-38 except that each of the liquid crystal aligning agents described in Table 7 was used in the above Example IE-38, the vertical alignment type liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 7.

&Lt; Evaluation of Physical Properties of Coating Film &

Examples IE-120 to 131

Evaluation of i-ray absorption and evaluation of heat resistance were carried out in the same manner as in Examples IE-67 to 93 except that the liquid crystal aligning agent described in Table 8 was used, respectively.

The evaluation results are shown in Table 8.

<Synthesis of radiation-sensitive polyorganosiloxane>

Example IE-132

5.0 g of EPS-4 synthesized in Synthesis Example 4 was used instead of EPS-1 as the polyorganosiloxane having an epoxy group in the above Example IE-1, and the compound (2-2- IE-9 was obtained in the same manner as in Example IE-1, except that the amount of the epoxy group-containing polyorganosiloxane (1-1 (2)) used was changed to 50 mol% . The weight average molecular weight Mw of S-IE-9 was 16,200.

Example IE-133

(2-2-1-1 (2)) was substituted for the epoxy group of EPS-1 in place of the compound (2-2-1-1 (1)) in the above Example IE-1 and 50% The preparation was carried out in the same manner as in Example IE-1, except that a mixture containing 5 mol% of the compound represented by the above formula (4-3-1) as the pretilt angle-expressing compound with respect to the epoxy group of EPS-1 was used Whereby a radiation-sensitive polyorganosiloxane S-IE-10 was obtained. The weight average molecular weight Mw of S-IE-10 was 18,400.

Examples IE-134 to 141

In the same manner as in Example IE-133 except that the kind and amount of the cinnamic acid derivative (1) and other pretilt angle-expressing compounds were changed as shown in Table 9, respectively, in the above Example IE-133, To obtain the polyorganosiloxanes S-IE-11 to S-IE-18, respectively. The weight average molecular weights Mw of these radiation-sensitive polyorganosiloxanes are shown in Table 9.

In Table 9, the abbreviations "(4-3-1)", "(4-3-2)" and "(4-3-3)" of the other pretilt angle- -3-1), (4-3-2), or (4-3-3).

&Lt; Production of liquid crystal aligning agent and evaluation of storage stability >

Examples IE-142-171

In the same manner as in Example IE-9 except that the kind of the radiation-sensitive polyorganosiloxane and the kind and the amount of the other polymer were changed as shown in Table 10, the liquid crystal aligning agent A -IE-42 to A-IE-71, respectively. Table 10 shows the evaluation results of the storage stability of each liquid crystal aligning agent measured in the same manner as in Example IE-9.

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

Examples IE-172 to 201

In the same manner as in Example IE-38 except that the liquid crystal aligning agent described in Table 11 was used in the above Example IE-38, the vertical alignment type liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 11.

&Lt; Evaluation of Physical Properties of Coating Film &

Examples IE-202 to 231

Evaluation of i-ray absorption and evaluation of heat resistance were carried out in the same manner as in Examples IE-67 to 93 except that the liquid crystal aligning agent described in Table 12 was used, respectively.

The evaluation results are shown in Table 12.

As clearly understood from the above examples, the liquid crystal aligning agent of the present invention is superior in liquid crystal aligning property and electrical characteristic to a liquid crystal aligning agent which is conventionally known as a liquid crystal aligning agent to which a photo alignment method can be applied Can be formed. In addition, since the liquid crystal alignment film obtained has high heat resistance without causing a photoreaction by light having a long wavelength range, for example, a wavelength of 365 nm or more, the liquid crystal panel can be manufactured without process problems. Further, since the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention does not cause a photoreaction by the light in the long wavelength region, it has long-term stability against light of the backlight when the liquid crystal panel is used.

Accordingly, when this liquid crystal alignment film is applied to a liquid crystal display device, the liquid crystal display device can be manufactured at a lower cost than in the past, and the obtained liquid crystal display device is excellent in various performances such as display characteristics and reliability. Accordingly, these liquid crystal display elements can be effectively applied to various apparatuses and can be suitably used for devices such as a desk calculator, a wristwatch, a desk clock, a coefficient display board, a word processor, a personal computer, a liquid crystal television, and the like.

Claims (9)

A compound represented by the following formula (1)
At least one member 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
Wherein the liquid crystal aligning agent contains a radiation-sensitive polyorganosiloxane.
&Lt; Formula 1 >

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group, provided that when R ³ is not a hydrogen atom, at least one of R ¹ and R ² has a carboxyl group or a carboxyl group And R < ¹ > and R &lt; ² &gt; may be bonded to each other to form a ring)
&Lt; General Formula (S-1)

(In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group and Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) The liquid crystal aligning agent according to claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 2 or a compound represented by Formula 3 below.
(2)

(Wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group, provided that at least one of R ⁴ and R ⁵ is an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, A group having an alicyclic group having 3 to 40 carbon atoms which is unsubstituted or substituted with a fluorine atom, and R ⁴ and R ⁵ may be bonded to each other to form a ring)
(3)

(Wherein R ⁶ is a single bond or a divalent organic group; R ⁷ is a hydrogen atom or a monovalent organic group; R ⁶ and R ⁷ may be bonded to each other to form a ring; R ⁸ is an unsubstituted An alkyl group having 1 to 20 carbon atoms which is substituted with a fluorine atom or an alicyclic group having 3 to 40 carbon atoms which is unsubstituted or substituted with a fluorine atom) The liquid crystal aligning agent according to claim 1, wherein X ¹ in the formula (S-1) is a group represented by the following formula (X ¹ -1) or (X ¹ -2).

The liquid crystal aligning agent according to any one of claims 1 to 3, further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide. The liquid crystal aligning agent according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of polysiloxane represented by the following formula (S-2), a hydrolyzate thereof and a condensate of a hydrolyzate .
&Lt; Formula (S-2)

(In the formula (S-2), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Y ² is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms Practical skill) A method for forming a liquid crystal alignment film, comprising applying a liquid crystal aligning agent according to any one of claims 1 to 3 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 aligning agent according to any one of claims 1 to 3. A compound represented by the following formula (1)
At least one member 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
Wherein the radiation-sensitive polyorganosiloxane is obtained by reacting a polyorganosiloxane with an organosilicon compound.
&Lt; Formula 1 >

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group, provided that when R ³ is not a hydrogen atom, at least one of R ¹ and R ² has a carboxyl group or a carboxyl group And R < ¹ > and R &lt; ² &gt; may be bonded to each other to form a ring)
&Lt; General Formula (S-1)

(In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group and Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) A compound represented by the following formula (1).
&Lt; Formula 1 >

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent organic group, provided that when R ³ is not a hydrogen atom, at least one of R ¹ and R ² has a carboxyl group or a carboxyl group And R &lt; ¹ &gt; and R &lt; ² &gt; may be bonded to each other to form a ring)