KR101450942B1 - Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

(화학식 1 중, Y¹은 수산기, 탄소수 1 내지 10의 알콕실기, 탄소수 1 내지 20의 알킬기 또는 탄소수 6 내지 20의 아릴기임)The present invention relates to a thermosetting resin composition comprising at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the following formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate, and at least one selected from the group consisting of an alkenyl group and an alkynyl group And a liquid crystal aligning agent containing a radiation-sensitive polysiloxane.
≪ Formula 1 >

(Wherein 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)

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, if a liquid crystal alignment film is formed by the rubbing process, dust or static electricity easily occurs in the process, and 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. Further, in a liquid crystal display device which is expected to be more highly dense in the future, irregularities are generated on the surface of the substrate due to high density of pixels, so that it is difficult to uniformly perform rubbing treatment.

As another means for orienting the liquid crystal in the liquid crystal cell, there is a method of aligning a liquid crystal alignment film by irradiating polarized or unpolarized radiation to a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface, The law 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 angle is usually given by inclining the direction of incidence of the irradiated radiation on the substrate surface from the normal of the substrate.

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, it is necessary to irradiate the optical axis of the light beam, which is inclined from the substrate normal line, to 10,000 J / m 2 or more in order to obtain a sufficient pretilt angle (See Japanese Patent Application Laid-Open Nos. 2002-250924 and 2004-83810 and J. of the SID 11/3, 2003, p.579).

The object of the present invention is to provide a liquid crystal aligning agent which provides a liquid crystal alignment film having good liquid crystal aligning ability even at a low exposure dose by irradiating polarized light or unpolarized light without rubbing treatment, And a liquid crystal display element excellent in various performances such as a method of producing an orientation film, display characteristics, reliability and the like.

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

At least one selected from the group consisting of a polysiloxane having a repeating unit represented by the following formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate,

A cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group

And a liquid crystal aligning agent containing a radiation-sensitive polysiloxane.

(Wherein 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,

The above liquid crystal aligning agent is applied to form a coating film, and the coating film is irradiated 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.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention comprises at least one (hereinafter referred to as "polysiloxane (1)") selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate, and,

A cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group

To obtain a radiation-sensitive polysiloxane.

[Polysiloxane (1)]

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

Examples of the alkoxyl group having 1 to 10 carbon atoms for Y ¹ in the above formula (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-heptadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, N-nonadecyl, n-eicosyl and the like; Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and the like.

The polysiloxane (1) may be any of linear, ladder, cage, cubic, and random types, or may have two or more of these structures in one molecule, or two or more types of structures having different structures It may also be a mixture of polysiloxanes.

The polysiloxane (1) preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 200 to 150,000, more preferably 200 to 100,000, and still more preferably 1,000 to 10,000.

Examples of the polysiloxane (1) particularly preferably used in the present invention include cubic-type octakis (high-hydrosilsesquioxane) represented by the following formula (1-1), the following formulas (1-2) to -6), and the like. As the polysiloxane (1) used in the present invention, a compound represented by the following formula (1-1) is preferable.

(Wherein n1 and n2 are each an integer of 3 to 8, n3 and n5 are each an integer of 1 to 50, n4 and n6 are each an integer of 0 to 1,000, and n7 is an integer of 5 to 10)

The polysiloxane (1) preferably used in the present invention preferably has a polysiloxane weight corresponding to 1 mol of the amount of the silicon-hydrogen bond of 50 to 5,000 g / mol, and more preferably 50 to 500 g / mol.

Octakis (high-hydrosilsesquioxane) represented by the above-mentioned formula (1-1) particularly preferable as the polysiloxane (1) used in the present invention can be obtained, for example, by the method described in Journal of American Chemical Society, , P.5586 (1970)].

As the polysiloxane (1) in the present invention, commercially available ones may be used. For example, the compound represented by the above formula (1-1) is available from TAL MATERIALS Inc.

[Derivatives of cinnamic acid]

The cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group used in the present invention is obtained by reacting at least one kind of group selected from the group consisting of an alkenyl group and an alkynyl group, May be a compound having a divalent group.

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

(단, "*"를 붙인 결합손이 R⁵-R⁶측임)로 표시되는 기이고, a는 0 내지 3의 정수이고, b는 0 내지 4의 정수임)Wherein R ¹ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group, with the proviso that some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, R ² is a single bond, an oxygen atom, -COO- or -OCO-, R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R ⁴ is a single bond, -COO- or * -OCO- (in which the bond with "*" is bonded to R ³ ), R ⁵ is a single bond, a methylene group or an alkylene group having 2 to 10 carbon atoms, and R ⁵ When R ⁶ is -CH = CH ₂ or -C≡CH and R ⁵ is a methylene group or an alkylene group, when R ⁶ is -CH = CH ₂ , -C≡CH or -OOC-CH = CH ₂ , R ⁷ is a fluorine atom or a cyano group, X ¹ is an oxygen atom or a group represented by the formula

(Provided that the bonding hand with "*" attached is R ⁵ -R ⁶ ), a is an integer of 0 to 3, and b is an integer of 0 to 4)

(단, "*"를 붙인 결합손이 R⁸과 결합함)로 표시되는 기이고, c는 0 내지 3의 정수이고, d는 0 내지 4의 정수임)Wherein R ⁸ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group, with the proviso that some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, R ⁹ is an oxygen atom, -COO- or -OCO-, R ¹⁰ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ¹¹ represents a single bond, -OCO- (CH _{2) e} - - or _{-O- (CH 2) g - *} ( so long as bond attached to "-" hand is combined with R ^12), provided only e, and g is an integer from 0 to 10, respectively, R ¹² is -CH = CH ₂ , -C≡CH or -OOC-CH = CH ₂ , R ¹³ is a fluorine atom or a cyano group, X ² is an oxygen atom,

(Provided that a bonding hand with "*" is bonded to R ⁸ ), c is an integer of 0 to 3, and d is an integer of 0 to 4)

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

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

Examples of the compound represented by the formula (2) include a cinnamic acid derivative having an alkenyl group represented by the following formulas (2-P1) to (2-P15) and (2-A1) to And the like;

(Wherein R ¹ has the same meaning as in the above formula (2), and i is an integer of 0 to 10)

Examples of the cinnamic acid derivative having an alkynyl group include the compounds represented by the following formulas (2-P16) to (2-P21), respectively.

(Wherein R ¹ has the same meaning as in the above formula (2), and f is an integer of 0 to 10)

The alkyl group having 1 to 40 carbon atoms represented by R ⁸ in the general formula (3) is, for example, an alkyl group having 1 to 20 carbon atoms, with the proviso that some or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom. Examples of such an alkyl group include those exemplified as the alkyl group of R ¹ in the above formula (2). Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ⁸ include a cholesteryl group, a cholestanyl group and an adamantyl group.

Examples of the divalent aromatic group, divalent heterocyclic group or divalent fused ring group of R ¹⁰ include a divalent aromatic group of R ³ , a divalent heterocyclic group or a divalent fused ring group in Formula 2 For example.

As the phenylene group of X ² , a 1,4-phenylene group is preferable.

Examples of the compound represented by the above formula (3) include a cinnamic acid derivative having an alkenyl group, for example, represented by the following formulas (3-P1) to (3-P5) and (3-A1) to And the like;

(Wherein R ⁸ has the same meaning as in the above formula (3), and h and j each represent an integer of 1 to 10)

Examples of the cinnamic acid derivative having an alkynyl group include compounds represented by the following formulas (3-P6) to (3-P8), (3-A4) and (3-A5).

(Wherein R ⁸ has the same meaning as in the above formula (3), and h and j each represent an integer of 1 to 10)

The compound represented by Formula 2 or 3 can be synthesized by a conventional method of organic chemistry.

For example, the compound represented by the above general formula (2-P1) can be produced by, for example, reacting hydroxycinnamic acid and a halogenated alkyl having an alkyl group corresponding to R ¹ by heating in the presence of a suitable base such as potassium carbonate, The compound is hydrolyzed with an appropriate aqueous alkali solution such as sodium hydroxide to give a cinnamic acid derivative having a carboxyl group and the carboxyl group is converted into a compound having a desired methylene chain CH ₂ ═CH (CH ₂ ) _k X '(wherein k is an integer of 1 to 6 And X 'is a halogen atom), preferably potassium carbonate.

The compound represented by the above formula (2-A1) can be prepared by reacting a carboxyl group of a cinnamic acid derivative having a carboxyl group synthesized in the same manner as described above with thionyl chloride to give an acid chloride, and then reacting this with hydroxyethyl acrylate In the presence of a suitable base catalyst such as triethylamine.

Compound represented by the compound and the formula (2-A2) represented by the formula (2-P2) is a cinnamic acid derivative having a carboxyl group, hydroxycinnamic alkyl carboxylic acid having an alkyl group corresponding to the acid and R ¹ (2-P1) or the compound represented by the above formula (2-A1), except that the compound obtained by reacting the compound of the formula (2-P1) with a compound obtained by reacting chloride in the presence of a suitable base such as potassium carbonate at a temperature of 0 캜 to room temperature. Can be obtained in the same manner as in the synthesis of the compound.

Compound represented by the compound and the formula (2-A4) represented by the formula (2-P4) is a cinnamic acid derivative having a carboxyl group, a hydroxy benzoic acid alkyl halide or soil having an alkyl group corresponding to methyl and R ¹ The alkylated alkyl is reacted in the presence of a suitable base such as potassium carbonate at a temperature of from room temperature to 100 ° C and then hydrolyzed with an appropriate alkaline aqueous solution such as sodium hydroxide to give an acid chloride with thionyl chloride, (2-P1) or a compound represented by the above formula (2-A1), respectively, except that the compound obtained by reacting the compound with the hydroxycinnamic acid in the presence of a suitable base at a temperature of 0 ° C to room temperature is used instead of the compound Can be obtained in the same manner as in the synthesis of the compound.

The compound represented by the above formula (2-P5) and the compound represented by the above formula (2-A5) are a cinnamic acid derivative having a carboxyl group, wherein an alkylcarboxylic acid chloride having an alkyl group corresponding to R ¹ and hydroxybenzoic acid In the presence of a suitable base such as triethylamine at a temperature of 0 ° C to room temperature and then converting the resulting product into an acid chloride by thionyl chloride and reacting the resulting product with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C to room temperature Can be obtained in the same manner as in the synthesis of the compound represented by the formula (2-P1) or the compound represented by the formula (2-A1), respectively, except that the compound obtained by reacting the compound represented by the formula

The compound represented by the above formula (2-P6) and the compound represented by the above formula (2-A6) can be synthesized by using a cinnamic acid derivative having a carboxyl group as the acid chloride by 4-alkylbenzoic acid with thionyl chloride, (2-P1) or the compound represented by the above formula (2-A1), respectively, except that the compound obtained by the reaction is reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium or the like at a temperature of 0 ° C to room temperature. Can be obtained in the same manner as in the synthesis of the compound represented by the formula (1).

The compound represented by the general formula and the compound (2-A15) represented by the formula (2-P15) is a cinnamic acid derivative having a carboxyl group, 4-hydroxy-cyclohexyl-carboxylic acid methyl and alkyl group corresponding to R ¹ Is reacted in the presence of a suitable alkali such as sodium hydride or sodium metal to give an ether which is then hydrolyzed with an aqueous alkali solution such as sodium hydroxide to give the thionyl chloride chloride, which is then reacted with potassium carbonate (2-P1) or a compound represented by the above formula (2-A1), respectively, except that the compound obtained by reacting the compound with the hydroxycinnamic acid in the presence of a suitable base at a temperature of 0 ° C to room temperature is used instead of the compound Can be obtained in the same manner as in the synthesis of the compound.

The compound represented by the above formula (2-P7) and the compound represented by the above formula (2-A7) are cinnamic acid derivatives having a quarboxylic group, wherein 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R ¹ (2-P1), except that a compound obtained by reacting a compound of the formula (2-P1) with thionyl chloride with an acid chloride in the presence of a suitable base such as potassium carbonate at a temperature of from 0 째 C to room temperature Can be obtained in the same manner as in the synthesis of the displayed compound or the compound represented by the above formula (2-A1).

The compound represented by the above general formula (2-P8) and the compound represented by the above general formula (2-A8) are derivatives of a cinnamic acid having a carboxyl group, in which a halogenated alkyl equivalent to R ¹ and a hydroxybenzaldehyde are reacted with a base such as potassium carbonate (2-P1) or the compound represented by the above formula (2-A1), except that a compound obtained by reacting the compound of the formula (2-P1) with a compound obtained by forming an ether bond and then aldol condensation of 4-acetylbenzoic acid in the presence of sodium hydroxide is used. ) Can be obtained in the same manner as the synthesis of the compound represented by the formula (1). Compounds represented by the above formulas (2-A9) to (2-A14) and (2-P9) to (2-P14) can also be obtained by a method analogous thereto.

The compound represented by the above formula (3-P1) and the compound represented by the above formula (3-A1) are derivatives of cinnamic acid having a carboxyl group and include 4-iodophenol and alkyl acrylate having an alkyl group corresponding to R ¹ (Generally referred to as a " Heck reaction ") with palladium and an amine as catalysts, and then ring-opening a desired cyclic acid anhydride such as succinic anhydride or glutaric anhydride to the reaction product Can be obtained in the same manner as in the synthesis of the compound represented by the above formula (2-P1) or the compound represented by the above formula (2-A1), respectively.

The compound represented by the formula (3-P2) and the compound represented by the formula (3-A2) are cinnamic acid derivatives having a carboxyl group, wherein 4-alkyl acetophenone corresponding to R ¹ and 4-formylbenzoic acid Can be obtained in the same manner as in the synthesis of the compound represented by the above formula (2-P1) or the compound represented by the above formula (2-A1), respectively, except that the compound obtained by aldol condensation in the presence of sodium hydroxide is used. The compound represented by each of the above formulas (3-P3) and (3-A3) can also be obtained by a method similar thereto.

[Sensitizing radiation-sensitive polysiloxane]

The radiation-sensitive polysiloxane contained in the liquid crystal aligning agent of the present invention can be prepared by reacting the polysiloxane (1) and the cinnamic acid derivative as described above with a hydrosilylation reaction, preferably in the presence of a catalyst, preferably in an organic solvent And the resulting polyorganosiloxane.

The cinnamic acid derivative 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 silicon-hydrogen bond of the polysiloxane (1).

As the catalyst, those known as catalysts for the hydrosilylation reaction can be used, and for example, compounds or complexes containing platinum, rhodium or palladium can be used. Of these, compounds or complexes containing platinum are preferable, and specific examples thereof include hexachloroplatinic acid (IV) hexahydrate, platinumcarbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane Complex, platinum-octylaldehyde / octanol complex, and the like. The above platinum compound or complex may be carried on a suitable carrier such as activated carbon. The amount of the catalyst to be used is preferably 0.01 to 10,000 ppm, more preferably 0.1 to 100 ppm, based on the weight of the cinnamic acid derivative used as the amount of the metal atom contained in the compound or complex.

As the organic solvent usable for the hydrosilylation reaction of the polysiloxane (1) and the cinnamic acid derivative, an aromatic hydrocarbon or an ether is preferable, and specific examples thereof include toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, Diethyl ether, 1,4-dioxane, diphenyl ether and the like. The solvent is used in an amount such that the solid concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight.

The reaction temperature is preferably room temperature to 250 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 120 hours, more preferably 1 to 10 hours.

When the polysiloxane (1) and the cinnamic acid derivative are reacted in the synthesis of the radiation-sensitive polysiloxane, a part of the cinnamic acid derivative may be substituted by an unsaturated compound having an epoxy group. When the cinnamic acid derivative and the unsaturated compound having an epoxy group are used in combination, the radiation-sensitive polysiloxane crosslinkable group can be introduced, and the strength of the resulting liquid crystal alignment film can be further improved. In this case, the synthesis of the radiation-sensitive polysiloxane is preferably carried out by reacting the polysiloxane (1) with a mixture containing a cinnamic acid derivative and an unsaturated compound having an epoxy group.

Examples of such an unsaturated compound having an epoxy group include allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, glycidyl acrylate, 4-vinyl-1-cyclohexene 1,2-epoxide, and the like. When a cinnamic acid derivative and an unsaturated compound having an epoxy group are used in combination, the use ratio of the unsaturated compound having an epoxy group is preferably 50 mol% or less based on the total amount of the unsaturated compound having a cinnamic acid derivative and an epoxy group.

[Other ingredients]

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

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

The other polymer can be used to further improve the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. These other polymers include, for example, at least one polymer selected from the group consisting of polyamic acid and polyimide; (Hereinafter, also referred to as "another polysiloxane") selected from the group consisting of a polysiloxane having a repeating unit represented by the following formula (4), a hydrolyzate thereof and a condensate of a hydrolyzate; Poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like can be given as examples of the poly (meth) acrylate ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative.

(Wherein X 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, and Y ² is an hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms)

[Polyamic acid]

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

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the 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- 3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetra 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7- Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ , 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] , 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ Dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 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, and tetracarboxylic acid dianhydrides represented by the following formulas (T-1) to (T-14) Alicyclic tetracarboxylic acid dianhydride;

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 tetracarboxylic dianhydrides represented by the following formulas (T-15) to (T-18), and the like.

Of these, 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 dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 - (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 [1,2-c] furan-1,3-dione, 1,3,3a, 4,5, (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- 3'- (tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- Malic acid Sumul, 3,5,6-tree-carboxy-2-carboxymethyl norbornane 2: 3,5: 6-dianhydride, 4,9- dioxa-tricyclo [5.3.1.0 ^2,6] undecane-3, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylate Acid dianhydride, 2,3 ', 2,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and the above-mentioned formulas (T-1), (T- 2) and (T-15) to (T-18), respectively. These tetracarboxylic acid dianhydrides are preferred from the viewpoint of being able to exhibit good liquid crystal alignability.

Particularly preferred tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5 , 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3- 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and pyromellitic acid dianhydride.

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

Examples of the diamine compound used in the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4 , 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4 , 4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- Phenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether , 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluorope (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7- Diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'- , 2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 4,4'-diaminobiphenyl, 1,4,4 '- (p-phenylene isopropylidene) bisaniline, 4,4' - (m-phenyleneisopropylidene) , 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'- diamino-2,2'-bis (trifluoromethyl ) Biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl and the like Aromatic diamines;

But are not limited to, 1,1-hexanediol, 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanedanilinedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (Cyclohexylamine), and 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) Diaminobenzene), 8- (4-chalconyloxy) octyloxy (2,4-diamino benzene), 6- (4'-fluoro-4-chalconyloxy) Benzene), 8- (4'-fluoro-4-chalconyloxy) octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, -2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy- Diaminobenzene, 1-cholestearyloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzoyl) (3,5-diaminobenzoyl), octadecyloxy (3,5-diamino benzoyl), hexadecyloxy (3,5-diaminobenzoyl) Benzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3, (2,4-diaminophenoxy) -4-trifluoro-3-methylpentanoate, (2,4-diaminophenoxy) Methyl benzoate, and diamine compounds represented by the following formulas (D-1) to (D-5);

Aromatic diamines having a hetero atom such as diaminotetraphenylthiophene;

1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, 1,4-diaminoheptamethylene diamine, Diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanedanilinedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4 , 4'-methylenebis (cyclohexylamine), and alicyclic diamines;

And diaminoorganosiloxanes such as diaminohexamethyldisiloxane and the like.

Among them, preferable examples include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'- 4,4'- (p-phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- Hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestearyloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy Diaminobenzoyl), cholestanyloxy (3,5-diamino benzoyl), cholestanoloxy (3,5-diaminobenzoyl) Diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine and the diamine compounds represented by the above formulas (D-1) to (D-5).

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

The proportion of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amino group contained in the diamine compound , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The synthesis reaction time is preferably 0.5 to 24 hours, more preferably 2 to 10 hours. 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 dimethyl sulfoxide,? -Butyrolactone, tetramethyl urea, and hexamethylphosphotriamide; m-cresol, xylenol, phenol, halogenated phenol and the like. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. When the organic solvent is used in combination with a poor solvent to be described later, the amount (a) of the organic solvent means the total amount of the organic solvent and the poor solvent.

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 methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, isoamyl isobutyrate, isoamyl propionate, methyl methoxy propionate, ethyl ethoxypropionate Propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol-diethyl ether, diethylene glycol, Dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4- Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisopentyl ether and the like.

When a poor solvent is used for a part of the organic solvent used in the synthesis of the polyamic acid, the use ratio thereof can be appropriately set within a range in which the polyamic acid to be purified is not precipitated, but it is preferable that the total amount of the organic solvent and the poor solvent Is 80% by weight or less, and more preferably 50% 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 is obtained by dehydrating and ring closure of the polyamic acid as described above to imidize it. At this time, all of the amic acid units contained in the polyamic acid may be dehydrated and ring closed, or only a part of the amic acid units may be dehydrated and cyclized to form a partial imide, in which the amic acid unit and the imide ring coexist. The imidization ratio of the polyimide is preferably 80% or more, and more preferably 85% or more. Here, the "imidization rate" means the ratio of the number of imide ring units to the sum of the number of amic acid units and the number of imide ring units in the polymer as a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation rate can be calculated from the spectrum of ¹ H-NMR measured at room temperature using tetramethylsilane as a reference material by dissolving the polyimide in an appropriate solvent and by using the following equation (1).

[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)

The dehydration ring closure reaction of polyamic acid can be carried out by a method comprising the steps of (i) heating the polyamic acid, (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring- Lt; / RTI &gt;

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 unit contained in the polyamic acid. 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 the 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 1 to 48 hours, more preferably 2 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 above method (ii), a reaction solution containing polyimide is obtained as described above. 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.

- polyamic acid and polyimide-terminated polyimide-

The polyamic acid and the polyimide may be of a terminally modified type having a controlled molecular weight. Such a terminal modification type can be synthesized by adding an appropriate molecular weight regulator such as an acid anhydride, a monoamine compound, or a monoisocyanate compound to the reaction system in the synthesis of polyamic acid. 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.

When the above-mentioned molecular weight modifier is used in the synthesis of polyamic acid, the amount of the molecular weight modifier is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the diamine.

- Solution viscosity of polyamic acid and polyimide -

The polyamic acid is preferably a solution of 10 wt% of N-methyl-2-pyrrolidone and has a viscosity of 20 to 800 mPa · s measured at 25 ° C. using an E-type rotational viscometer, preferably 30 to 500 mPa 占 퐏.

The polyimide preferably has a solution viscosity of 20 to 800 mPa · s and a viscosity of 30 to 500 mPa · s at 25 ° C. using an E-type rotational viscometer with a 10% by weight γ-butyrolactone solution. Is more preferable.

[Other polysiloxane]

At least one (other polysiloxane) selected from the group consisting of polysiloxane having a repeating unit represented by the above-mentioned formula (4), a hydrolyzate thereof and a condensate of a hydrolyzate is preferably at least one selected from the group consisting of polystyrene- The weight average molecular weight is preferably 500 to 50,000, more preferably 500 to 5,000. The other polysiloxane is preferably a condensate of a hydrolyzate of a polyorganosiloxane in which at least a part of X in the general formula (4) is an alkyl group having 1 to 20 carbon atoms and at least a part of Y ² is an alkoxyl group having 1 to 10 carbon atoms Do.

The other polysiloxane is preferably at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as "raw silane compound"), preferably in the presence of water and a catalyst Can be synthesized by hydrolysis or hydrolysis and condensation.

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, i-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, ;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 -Diketone compounds such as heptanedione, and the like. These ketone compounds may be used singly 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 alone 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, meqic 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.

When the liquid crystal aligning agent of the present invention contains other polymers together with the above radiation-sensitive polysiloxane, 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 polysiloxane. The more preferable content of the other polymer differs depending on the kind of the other polymer.

In a 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 polysiloxane and a polyamic acid and a polyimide, a more preferable ratio of both of them is 100 parts by weight of a radiation-sensitive polysiloxane The total amount of the polyamic acid and the polyimide 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 polysiloxane and another polysiloxane, a more preferable ratio of use is 100 to 2,000 parts by weight as the amount of the other polysiloxane relative to 100 parts by weight of the radiation- .

When the liquid crystal aligning agent of the present invention contains another polymer together with the radiation-sensitive polysiloxane, the kind of the other polymer is preferably at least one polymer selected from the group consisting of polyamic acid and polyimide, or other polysiloxane .

[Heat-sensitive crosslinking agent]

The thermosensitive cross-linking agent can be used for stabilizing the pre-tilt angle and for improving the film strength. As the heat-sensitive crosslinking agent, polyfunctional epoxy compounds are effective. Examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether , 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis N, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, N'- N-diglycidylaminomethylcyclohexane, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl A glycidyl ester-based epoxy resin, glycidyl diamine-based epoxy resin, heterocyclic epoxy resin, an acrylic resin having an epoxy group and the like. (Commercially available from Japan Epoxy Resins Co., Ltd.), Epolite 400E, Epol 3002 (manufactured by Kyotosha Chemical Co., Ltd.), Epikote 828, Epoxy 152, Epoxy novolak 180S May be mentioned as desirable. When a polyfunctional epoxy compound is used as a heat-sensitive crosslinking agent, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of effectively causing a crosslinking reaction.

When the liquid crystal aligning agent of the present invention contains a heat-sensitive crosslinking agent, its content is preferably 100 parts by weight or less based on 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polysiloxane and optionally other polymer, Is not more than 50 parts by weight.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- Diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. And a reaction product of a tetracarboxylic acid dianhydride and a silane compound having an amino group described in Patent Document 17 (Japanese Patent Laid-Open Publication No. 63-291922).

When the liquid crystal aligning agent of the present invention contains a functional silane compound, its content is preferably 50 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polysiloxane and other polymer optionally used By weight or less.

〔Surfactants〕

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicon surfactant, a polyalkylene oxide surfactant, and a fluorine-containing surfactant.

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.

[Production of liquid crystal aligning agent]

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

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

The organic solvent preferably usable in the liquid crystal aligning agent of the present invention differs depending on the kind of the other polymer to which it is optionally 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 polysiloxane and a polyamic acid and a polyimide, preferred organic solvents are those used for the synthesis of polyamic acid, Organic solvents. At this time, the poor solvent exemplified for use in the synthesis of the polyamic acid of the present invention may be used in combination.

Particularly preferred organic solvents include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, diisobutylketone, Methyl-2-pentanone, diisopentyl ether, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, isoamyl propionate, isoamyl isobutyrate, methyl methoxy propionate, ethyl N-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethyleneglycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid Sites, D. and the like can be mentioned ethylene glycol monoethyl ether acetate.

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

On the other hand, as the organic solvent in the case where the liquid crystal aligning agent of the present invention contains only the radiation-sensitive polysiloxane as the polymer or the radiation-sensitive polysiloxane and the other polysiloxane, for example, 1-ethoxy-2- 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, dipropylene glycol dimethyl ether, ethylene Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate , Ethyl cellosolve acetate, Butyl acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid sec Butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, , Amyl acetate, and acetic acid isoam wheat. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate or sec-

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

The solid concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., %. The liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film . On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating properties are sometimes insufficient. A particularly preferable range of the solid concentration of the liquid crystal aligning agent of the present invention varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. 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 of forming the liquid crystal alignment film, for example, a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate, and then giving the liquid crystal aligning ability to the coating film by a photo alignment method.

First, the liquid crystal aligning agent of the present invention is coated on the transparent electroconductive film side of a substrate provided with a patterned transparent electroconductive film by a suitable coating method such as a roll coater method, a spinner method, a printing method, or an ink jet method, To 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 glass such as float glass and soda glass, transparent substrates including plastics such as 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.

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

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

As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. The ultraviolet rays in the above-mentioned preferable wavelength range can be obtained by a means for using the light source in combination with a filter, a diffraction grating or the like.

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, and further, 1,000 J / m 2 or less. It is available for reduction.

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

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element of the present invention comprises a liquid crystal alignment layer formed from the liquid crystal aligning agent of the present invention. The liquid crystal display element of the present invention can be produced, for example, as follows.

A pair of substrates on which a liquid crystal alignment film is formed as described above are prepared, the liquid crystal alignment film of the liquid crystal alignment film is faced to each other so that the polarization direction of the irradiated linearly polarized radiation is at a predetermined angle, the peripheral portion between the substrates is sealed with a sealant , 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 that the liquid crystal cell is heated to a temperature at which the liquid crystal used takes an isotropic phase, and then cooled to room temperature to remove the flow orientation at the time of injection.

Further, a polarizing plate is bonded to both sides of the polarizing plate so that the polarizing direction of the polarizing plate is at a predetermined angle with the easy axis of alignment of the liquid crystal alignment film of the substrate, respectively. 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, a nematic liquid crystal having a positive dielectric anisotropy is preferable, and examples thereof include biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, A cyclohexane-based liquid crystal, a pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a quartz-based liquid crystal, or 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 vertically aligned liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and examples thereof include a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff salt mechanical liquid crystal, Biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, 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 of the present invention thus manufactured is excellent in various performances such as display characteristics and reliability.

[Example]

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

The weight average molecular weight in the following examples 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 / ㎠

&Lt; Synthesis of cinnamic acid derivative >

Synthesis Example P (1)

Compound (2-P4-1) was synthesized according to Reaction Scheme 1 below.

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 1- 99.7 g of pentane was added and the reaction was carried out at 100 占 폚 for 5 hours with stirring. After completion of the reaction, reprecipitation was performed with water. Subsequently, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 104 g of white crystals of the compound (2-P4-1-1).

104 g of the compound (2-P4-1-1) was taken in a reaction vessel, to which 1 L of thionyl chloride and 770 μL of N, N-dimethylformamide were added, and the mixture was stirred at 80 ° C for 1 hour. Then, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, the mixture was washed with an aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate and concentrated, and then tetrahydrofuran was added to form a solution.

Then, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 mL of tetrahydrofuran, and 1 L of water were added to a 5 L three-necked flask which was separate from the above. This aqueous solution was ice-cooled, and a tetrahydrofuran solution containing a reaction product of the above compound (2-P4-1-1) and thionyl chloride was slowly added dropwise and the reaction was further carried out for 2 hours with stirring. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize and extracted with ethyl acetate. The extract was dried with magnesium sulfate, concentrated and recrystallized with ethanol to obtain a white crystal of compound (2-P4-1-2) &Lt; / RTI &gt;

42.3 g of the compound (2-P4-1-2) synthesized above, 41.5 g of potassium carbonate, 5.00 g of potassium iodide, 4-bromo-1-butene And 600 mL of 1-methyl-2-pyrrolidone were charged, and the reaction was carried out under nitrogen at 90 占 폚 for 3 hours with stirring. After completion of the reaction, toluene and water were added to extract, and the organic layer was dried over magnesium sulfate, concentrated, and recrystallized from methanol to obtain 35 g of a compound (2-P4-1).

Synthesis Example P (2)

Compound (3-P5-1) was synthesized according to Reaction Scheme 2 below.

A 5 L three-necked flask equipped with a thermometer and a nitrogen inlet tube was charged with 44 g of 4-iodophenol, 32 g of hexyl acrylate, 28 mL of triethylamine, 4.6 g of tetrakis (triphenylphosphine) palladium, 2 L was added thereto, and the inside of the system was sufficiently dried. Subsequently, the system was heated to 90 占 폚 and the reaction was carried out under stirring in a nitrogen stream for 2 hours. After completion of the reaction, dilute hydrochloric acid was added, and the organic layer was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, concentrated, and recrystallized with ethanol to obtain 24 g of a compound (3-P5-1-1).

24 g of the compound (3-P5-1-1) synthesized above, 11.0 g of succinic anhydride and 1.2 g of 4-dimethylaminopyridine were placed in a 500 mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube, The inside of the system was sufficiently dried. To this system, 11.2 g of triethylamine and 200 mL of tetrahydrofuran were added, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, diluted hydrochloric acid was added, and the organic layer was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 17.4 g of a compound (3-P5-1-2).

10.4 g of the compound (3-P5-1-2) synthesized as described above, 10.4 g of potassium carbonate, 1.25 g of potassium iodide, 5.58 g of 4-butyl-1-butene 5.58 g and 1-methyl-2-pyrrolidone (150 mL), and the reaction was carried out under nitrogen at 90 DEG C for 3 hours with stirring. After completion of the reaction, toluene and water were added to extract, and the organic layer was dried over magnesium sulfate, concentrated, and then recrystallized from methanol to obtain 8.5 g of compound (3-P5-1).

Synthesis Example P (3)

(2-P4-2) was obtained in the same manner as in Synthesis Example P (1) except that 20.0 g of allyl bromide was used instead of 4-bromo-1-butene in Synthesis Example P (1) (Compound (2-P4-2)).

&Lt; Synthesis of other polymer >

[Synthesis of polyamic acid]

Synthesis Example PA-1

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

Synthesis Example PA-2

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 14.23 g (0.1 mole) of cyclohexane bis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone, Lt; 0 &gt; C for 6 hours. The reaction mixture was then poured into excess 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 32 g of polyamic acid PA-2.

[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 solution in which 0.26 g of maleic anhydride prepared in 10.8 g of water was added to a separate flask having a capacity of 20 mL was added and heated and stirred 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 thereto and the mixture was concentrated again to obtain a polymer solution containing 10 wt% of polyorganosiloxane PS-1. The weight average molecular weight Mw of PS-1 was 5,100.

<Synthesis of radiation-sensitive polysiloxane>

Example CH-1

0.85 g of octakis (high-through-desilsesquioxane) (manufactured by TAL MATERIALS INC.), 8.97 g of the compound (2-P4-1) synthesized in Synthesis Example P (1), 80 mL of toluene, 100 μL of a xylene solution containing 2% by weight of a methyldisiloxane complex was added, and the reaction was carried out by refluxing under nitrogen for 20 hours. After completion of the reaction, the reaction product was redeposited with methanol. The precipitate was dissolved in ethyl acetate and washed with water. The solvent was distilled off to obtain 5.4 g of a white powder of radiation-sensitive polysiloxane S-CH-1.

Example CH-2

Except that in Example CH-1, a mixture of 4.49 g of the compound (2-P4-1) and 1.14 g of allyl glycidyl ether was used instead of 8.97 g of the compound (2-P4-1) 1 to obtain a radiation-sensitive polysiloxane S-CH-2.

Example CH-3

Except that 8.05 g of the compound (3-P5-1) synthesized in Synthesis Example P (2) was used instead of 8.97 g of the compound (2-P4-1) in Example CH- 1 was carried out in the same manner to obtain a radiation-sensitive polysiloxane S-CH-3.

Example CH-4

Example CH-1 was prepared in the same manner as in Example CH-1 except that 8.66 g of the compound (2-P4-2) synthesized in Synthesis Example P (3) was used instead of the compound (2- In the same manner, a radiation-sensitive polyorganosiloxane S-CH-4 was obtained.

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

Example CH-5

[Production of liquid crystal aligning agent]

100 parts by weight of the radiation-sensitive polysiloxane S-CH-1 obtained in the above Example CH-1 and 2,000 parts by weight of PA-1 as the other polymer in the solution containing the polyamic acid PA-1 obtained in the above Synthesis Example PA- N-methyl-2-pyrrolidone and butyl cellosolve were added to the mixture, and the solvent composition was adjusted to a ratio of N-methyl-2-pyrrolidone: butyl cellosolve = 50: (Weight ratio) and 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 A-CH-1.

The storage stability of the liquid crystal aligning agent A-CH-1 was evaluated according to the following methods and criteria, and the storage stability of the liquid crystal aligning agent A-CH-1 was "good ".

[Evaluation method of storage stability]

A coating film of a liquid crystal aligning agent was formed on a glass substrate by spin coating with varying the number of revolutions, and the number of revolutions at which the film thickness of the coating film after removal of the solvent became 1,000 ANGSTROM was examined.

Subsequently, a part of the liquid crystal aligning agent A-CH-1 was taken and stored at -15 캜 for 5 weeks. The liquid crystal aligning agent after preservation was visually observed. When the precipitation of insoluble matter was observed, the storage stability was judged as "defective ".

When insoluble matter was not observed after 5 weeks of storage, a coating film was formed on a glass substrate by spin coating at a revolution number of 1,000 Å before storage, and the film thickness after removal of the solvent was measured. When the film thickness was deviated by more than 10% from 1,000 ANGSTROM, the storage stability was judged as "defective ", and when the film thickness deviation was less than 10%, the storage stability was judged as" good ".

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

Examples CH-6 to 10, 15, 16 and 18

The liquid crystal aligning agents A-CH-2 to A-CH-6 and A-CH-6 were prepared in the same manner as in Example CH-5 except that the kind of the radiation-sensitive polysiloxane and the kind and the amount of the other polymer were changed as shown in Table 1. [ CH-11, A-CH-12 and A-CH-14, respectively.

Example CH-11

As another polymer, an amount corresponding to 2,000 parts by weight of PS-1 solids in the solution containing the other polysiloxane PS-1 obtained in Synthesis Example 5 was taken, and the amount of the radiation-sensitive polysiloxane S- 100 parts by weight of CH-1 was added, and 1-ethoxy-2-propanol was further added to obtain a solution having a solid content 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-CH-7.

Examples CH-12-14 and 17

CH-8 to A-CH-10 and A-CH-10 were prepared in the same manner as in Example CH-11, except that the kind of the radiation-sensitive polysiloxane and the kind and amount of the other polymer were changed as shown in Table 1. [ CH-13, respectively.

Example CH-19

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

The liquid crystal aligning agent A-CH-1 prepared in Example CH-5 was coated on the transparent electrode surface of the glass substrate with a transparent electrode including the ITO film using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute Then, the inside of the system was heated in an oven purged with nitrogen at 200 DEG C for 1 hour to form a coating film having a thickness of 0.1 mu m. Subsequently, 1,000 g / m 2 of polarized ultraviolet rays including a 313 nm bright line was irradiated from the direction of 40 ° from the substrate normal using an Hg-Xe lamp and a Glane Taylor prism on the surface of this coating film to form a liquid crystal alignment film. The same operation was repeated to prepare a pair of substrates (two substrates) each 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 peripheral portion 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 pressed against the substrate surface so that the projection direction was inverted, and the adhesive was heat-cured at 150 DEG C for 1 hour. Subsequently, a negative type liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then slowly cooled to room temperature. Subsequently, a polarizing plate was bonded to both outer sides of the substrate so that the polarization directions thereof were orthogonal to each other, and the angle of 45 degrees with respect to the projection direction of the ultraviolet optical axis of the liquid crystal alignment film with respect to the substrate surface.

This liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 2.

<Evaluation Method of Liquid Crystal Display Element>

(1) Evaluation of liquid crystal alignment property

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) to the liquid crystal display device manufactured as described above was observed under a microscope. Respectively.

(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 was applied to the liquid crystal display device manufactured as described above with 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 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 CH-20 to 33

A vertical alignment type liquid crystal display device was manufactured and evaluated in the same manner as in Example CH-19 except that the kind of the liquid crystal aligning agent used and the irradiation amount of the polarized ultraviolet ray at the time of forming the liquid crystal alignment film were changed as shown in Table 2, respectively. The results are shown in Table 2.

In Example 33, the light resistance was evaluated as follows, and the evaluation result was "good".

[Evaluation of light fastness in Example CH-33]

The initial voltage holding ratio of the liquid crystal display device manufactured as described above was measured under the same conditions as the evaluation of the voltage holding ratio. Thereafter, the liquid crystal display device was placed at a distance of 5 cm under a 40-watt white fluorescent lamp, irradiated with light for 1,000 hours, and then the voltage holding ratio was measured again under the same conditions as above. The light resistance was evaluated as "good" when the value of the voltage holding ratio was less than +/- 2% with respect to the initial value, and the " poor "

Comparative Example CH-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 the compound represented by the following formula (d-1) synthesized according to Japanese Patent Application Laid-Open No. 2003-520878, Was dissolved in 283.4 g of N-methyl-2-pyrrolidone, and the reaction was carried out 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 thus synthesized was dissolved in a mixed solvent of N-methyl-2-pyrrolidone and butyl cellosol (mixing ratio = 50: 50 (weight ratio)) to prepare a solution having a solid concentration of 3.0% by weight. This solution was filtered with a filter having an opening diameter of 1 占 퐉 to prepare a liquid crystal aligning agent R-CH-1.

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

A liquid crystal alignment film was formed in the same manner as in Example CH-19 except that the above-prepared liquid crystal aligning agent R-CH-1 was used, and a vertically aligned liquid crystal display device was produced and evaluated. The results are shown in Table 2.

Example CH-34

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

The liquid crystal aligning agent A-CH-11 prepared in Example CH-15 was coated on the transparent electrode surface of the transparent electrode-coated glass substrate including the ITO film using a spinner and prebaked on a hot plate at 80 DEG C for 1 minute Thereafter, the coating film was heated at 200 DEG C for 1 hour to form a coating film having a 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 a pair of glass substrates (two pieces) having the liquid crystal alignment film on the transparent conductive film surface.

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the peripheral portions of the surfaces of the pair of substrates on which the liquid crystal alignment films were formed by screen printing and then the substrates were stacked so that the polarizing ultraviolet 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. Then, the TN 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 orthogonal to each other and parallel to the polarization direction of the liquid crystal alignment film.

This liquid crystal display element was evaluated in the same manner as in Example CH-19, except that liquid crystal alignability, voltage retention rate and baking were evaluated. The results are shown in Table 3.

Examples CH-35 and 36

A TN alignment type liquid crystal display device was produced and evaluated in the same manner as in Example CH-34 except that the kind of the liquid crystal aligning agent used was changed as shown in Table 3. [ The results are shown in Table 3.

As clearly understood from the above examples, the liquid crystal aligning agent of the present invention not only has excellent storage stability but also has excellent liquid crystal alignability and electrical properties even with a smaller dose of radiation than conventionally known liquid crystal aligning agents for photoalignment A liquid crystal alignment film can be formed.

[Effects of the Invention]

The liquid crystal aligning agent of the present invention can form a liquid crystal alignment film having excellent liquid crystal alignability and electric characteristics even at a low dose of radiation, as compared with liquid crystal aligning agents conventionally known as liquid crystal aligning agents to which the photo alignment method can be applied. Accordingly, when this liquid crystal alignment film is applied to a liquid crystal display device, a liquid crystal display device can be manufactured at a lower cost than conventional ones, and various performances such as display characteristics and reliability are excellent. 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 (8)

At least one selected from the group consisting of a polysiloxane having a repeating unit represented by the following formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate,
A cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group
A radiation-sensitive polysiloxane obtained by reacting
At least one polymer selected from the group consisting of polyamic acid and polyimide
Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.
&Lt; Formula 1 >

(Wherein 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 cinnamic acid derivative is a compound having at least one group selected from the group consisting of an alkenyl group and an alkynyl group and a divalent group represented by the following formula.

3. The liquid crystal aligning agent according to claim 2, wherein the cinnamic acid derivative is a compound represented by the following formula (2) or a compound represented by the following formula (3).
(2)

Wherein R ¹ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group, with the proviso that some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, R ² is a single bond, an oxygen atom, -COO- or -OCO-, R ³ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R ⁴ is a single bond, -COO- or * -OCO- (in which the bond with "*" is bonded to R ³ ), R ⁵ is a single bond, a methylene group or an alkylene group having 2 to 10 carbon atoms, and R ⁵ When R ⁶ is -CH = CH ₂ or -C≡CH and R ⁵ is a methylene group or an alkylene group, when R ⁶ is -CH = CH ₂ , -C≡CH or -OOC-CH = CH ₂ , R ⁷ is a fluorine atom or a cyano group, X ¹ is an oxygen atom or a group represented by the formula

(Provided that the bonding hand with "*" attached is R ⁵ -R ⁶ ), a is an integer of 0 to 3, and b is an integer of 0 to 4)
(3)

Wherein R ⁸ is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group, with the proviso that some or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom, R ⁹ is an oxygen atom, -COO- or -OCO-, R ¹⁰ is a divalent aromatic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ¹¹ represents a single bond, -OCO- (CH _{2) e} - - or _{-O- (CH 2) g - *} ( so long as bond attached to "-" hand is combined with R ^12), provided only e, and g is an integer from 0 to 10, respectively, R ¹² is -CH = CH ₂ , -C≡CH or -OOC-CH = CH ₂ , R ¹³ is a fluorine atom or a cyano group, X ² is an oxygen atom,

(Provided that a bonding hand with "*" is bonded to R ⁸ ), c is an integer of 0 to 3, and d is an integer of 0 to 4) The liquid crystal composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the following formula (4), a hydrolyzate thereof and a condensate of a hydrolyzate Orientation agent.
&Lt; Formula 4 >

(Wherein X is a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and Y ² is an hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms) 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. delete delete