KR101778091B1 - Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

(Problem) It is an object of the present invention to provide a liquid crystal aligning property (pretilt angle manifesting property) which is excellent in coating property and printing property to a panel having elaborate concavities and convexities, can be imparted by a photo alignment method with a small radiation dose, And to provide a liquid crystal aligning agent which gives a liquid crystal alignment film.
(Solution) The liquid crystal aligning agent is a liquid crystal aligning agent comprising a polyorganosiloxane having a specific photosensitive structure, and tetracarboxylic acid dianhydride, an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, At least one member selected from the group consisting of a polyamic acid obtained by reacting a diamine having a group having a linked structure or a group having a steroid structure with a diamine containing a diamine having a carboxyl group and a polyimide obtained by dehydrocondensing the polyamic acid Lt; / RTI >

Description

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

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

In a liquid crystal display element, a liquid crystal alignment film is formed on a surface of a substrate in order to orient 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 in a direction in which the surface of the organic film is covered with rayon or the like. This is the same in a liquid crystal display element of a transverse electric field system. However, when the formation of the liquid crystal alignment film is performed by rubbing treatment, dust or static electricity is likely to be generated during the rubbing process, so that there is a problem that dust adheres to the surface of the alignment film to cause defective display. In addition, ) Device has a problem that the circuit breakage of the TFT element occurs due to the generated static electricity, which causes a decrease in the product yield. As another means for aligning the liquid crystal in the liquid crystal cell, there has been proposed a photo alignment method in which a liquid crystal alignment capability is imparted by irradiating polarized or unpolarized radiation to a radiation-sensitive organic thin film formed on the substrate surface (See Patent Documents 1 to 6). According to this optical alignment method, it is possible to form a uniform liquid crystal alignment without generating dust or static electricity during the process.

However, as the liquid crystal display element, liquid crystal display elements of a horizontal alignment mode using a nematic liquid crystal having positive dielectric anisotropy typified by TN (Twisted Nematic) type, STN (Super Twisted Nematic) (Homeotropic) alignment mode VA (Vertical Alignment) type liquid crystal display device using a nematic liquid crystal having negative dielectric anisotropy is known. 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 the normal direction of the substrate toward a certain direction. As a means for this, for example, a method of forming protrusions on the surface of a substrate, a method of forming a stripe on a transparent electrode, and a method of slightly obliquely tilting the liquid crystal molecules toward one direction in the substrate surface from the substrate normal direction by using a rubbing alignment film (Pre-tilting) method and the like are adopted. The above-described photo alignment method is also useful as a method for controlling the direction in which liquid crystal molecules are tilted in a liquid crystal display element of the vertical alignment mode. That is, it has been known that the orientation of liquid crystal molecules can be uniformly controlled at the time of voltage application by using a vertically-oriented liquid crystal alignment film in which alignment regulation ability and pretilt angularity are imparted by the photo alignment method 1, 2 and 4 to 6).

As described above, the liquid crystal alignment film produced by the photo alignment method can be effectively applied to various liquid crystal display elements. However, in order to impart the liquid crystal aligning ability to the organic thin film by the photo alignment method, it is necessary to irradiate strong radiation of 10,000 J / m < 2 > or more, and there arises a problem of deterioration of performance due to cutting of molecules constituting the organic thin film In addition, time-lapse deterioration of the radiation irradiation apparatus (for example, deterioration of the light irradiation intensity of the ultraviolet lamp over time) is serious, which is problematic from the viewpoint of reducing the production cost of the liquid crystal display element. Further, it has been pointed out that the liquid crystal alignment film formed by the photo alignment method may change its shape over time even if it has the desired pretilt angular expression at the beginning, and improvement is demanded.

In this regard, as a novel liquid crystal alignment film material capable of exhibiting good liquid crystal aligning performance with an extremely small irradiation dose when the photo alignment method is applied, a material comprising a polyamic acid or polyimide having a specific photosensitive site introduced into the molecule is reported (Patent Documents 7 to 9). The liquid crystal aligning agent described in these documents is an extremely excellent material capable of forming a liquid crystal alignment film exhibiting good liquid crystal alignability by irradiation of about 500 to 3,000 J / m 2.

However, in recent years, there has been a demand for a high demand for high-definition and high-speed responsiveness of a liquid crystal display device, and accordingly, improvements have been made on the hard surface such as a substrate configuration in order to meet this demand. For this reason, the requirement for the applicability and printability of the liquid crystal aligning agent has become more stringent than conventionally, in order to generate inevitably complicated steps on the substrate surface and ensure good visibility even in the stepped portion. Further, in a liquid crystal display device having a liquid crystal alignment film by a photo alignment method, after-image and burn-in may be a problem, and improvement thereof is desired. Particularly, the luminance difference generated on the screen due to the above-mentioned temporal change of the pretilt angle is recognized as a burn-in to the observer, and the improvement is urgent.

As described above, a liquid crystal aligning agent capable of forming the liquid crystal alignment film exhibiting the advantages of the photo alignment method advantageously with a small radiation dose and exhibiting improved afterimage and burn-in characteristics is not yet known. There is a strong demand for the provision of products.

Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Patent Application Laid-Open No. 2002-250924 Japanese Patent Application Laid-Open No. 2004-83810 Japanese Patent Application Laid-Open No. 9-211468 Japanese Patent Application Laid-Open No. 2003-114437 International Publication No. 2009/25385 pamphlet International Publication No. 2009/25386 pamphlet International Publication No. 2009/25388 brochure Japanese Patent Application Laid-Open No. 63-291922

 T. J. Scheffer et al. J. Appl. Phys. vol. 19, p2013 (1980)

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal display device which is excellent in applicability and printing property to a panel having fine irregularities, (Pre-tilt angularity) of the liquid crystal alignment film, and further provides a liquid crystal alignment film excellent in the burn-in property.

Another object of the present invention is to provide a liquid crystal display element having a liquid crystal alignment film excellent in burn-in characteristics formed by the liquid crystal aligning agent and excellent in long-term reliability.

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

The above objects and advantages of the present invention are achieved by firstly,

(A) a compound represented by the following formula (A1):

(In the formula (A1), R is a fluorine atom or a cyano group, a is an integer of 0 to 4, and " * "

A polyorganosiloxane having a structure represented by the following formula

(B) tetracarboxylic acid dianhydride and

(b2) a diamine containing a diamine having a carboxyl group and

At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a polyamic acid and a polyimide obtained by dehydrocondensing the polyamic acid

And a liquid crystal aligning agent. The diamine preferably further includes (b1) an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected, or a diamine having a group having a steroid structure.

The above objects and advantages of the present invention are secondly,

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

The liquid crystal aligning agent of the present invention can impart good liquid crystal alignability (pre-tilt angle manifestation) by the photo alignment method with a small radiation dose, as well as excellent applicability and printing property to the panel having the unevenness , And a liquid crystal alignment film excellent in after-image and burn-in characteristics can be provided.

The liquid crystal display element of the present invention comprising the liquid crystal alignment layer formed of the liquid crystal alignment agent of the present invention has improved burn-in characteristics and excellent long-term reliability, and display performance is not deteriorated even when used over a long period of time. Accordingly, the liquid crystal display element of the present invention can be effectively applied to various apparatuses, and can be used for various applications such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a portable information terminal, And can be suitably used for display devices such as various monitors and liquid crystal TVs.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

As described above, in the liquid crystal aligning agent of the present invention,

(A) a polyorganosiloxane having a structure represented by the formula (A1) (hereinafter also referred to as "polyorganosiloxane (A)")

(B) tetracarboxylic acid dianhydride and

(b2) a diamine containing a diamine having a carboxyl group and

(Hereinafter also referred to as " polyimide (B) ") obtained by reacting polyamic acid (hereinafter also referred to as polyimide (B) And contains one kind of polymer. The diamine preferably further includes (b1) an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected, or a diamine having a group having a steroid structure.

≪ Polyorganosiloxane (A) >

The polyorganosiloxane (A) in the present invention is a polyorganosiloxane having a structure represented by the formula (A1).

The "a" in the formula (A1) is preferably 0 or 1, and more preferably 0.

Examples of the structure represented by the formula (A1) include the following formulas (A1-1) and (A1-2):

(In the formulas (A1-1) and (A1-2), R, a and "*" have the same meanings as those in the formula (A1);

R ¹ in the formula (A1-1) is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, or an alkyl group having 1 to 40 carbon atoms, provided that a part or all of the hydrogen atoms of the alkyl group is a fluorine atom May be substituted,

X ¹ is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO- (in the above, a bonding hand having a "+" attached to R ¹ )

R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group,

X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO- (in the above, a bonding hand with a "+" attached to R ² )

b is an integer from 0 to 3;

In formula (A1-2), R ³ is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, or an alkyl group having 1 to 40 carbon atoms, provided that a part or all of the hydrogen atoms of the alkyl group is a fluorine atom May be substituted,

X ³ is an oxygen atom or a divalent aromatic group,

R ⁴ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group,

X ⁴ represents a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO- (in the above, a bonding hand having a "+" attached to R ⁴ )

and c is an integer of 0 to 3)

A group represented by each of R < 1 > and R < 2 >

Examples of a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group represented by R ³ in the formula (A1-1) and R ^{1 in} the formula (A1-2) include a cholesteryl group, A stanyl group, and an adamantyl group. The alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ³ is preferably an alkyl group having 1 to 20 carbon atoms (provided that a part or all of the hydrogen atoms of the alkyl group may be substituted 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.

By the formula (A1-1) R ² and the formula (A1-2) Examples of the divalent aromatic group of R ^4, for example, 1,4-phenylene, 2-fluoro-in of the 1,4 Phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group and the like;

Examples of the divalent alicyclic group represented by R ² and R ⁴ include 1,4-cyclohexylene group, 2-fluoro-1,4-cyclohexylene group, 3-fluoro-1,4-cyclohexylene 2,3,5,6-tetrafluoro-1,4-cyclohexylene group and the like;

Examples of the divalent heterocyclic group of R ² and R ⁴ include a 1,4-pyridylene group, a 2,5-pyridylene group and a 1,4-furanylene group;

Examples of the divalent condensed ring group of R ² and R ⁴ include a naphthylene group and the like.

The group represented by the formula (A1-1) is preferably a group represented by the formula:

(Wherein R < ¹ > and " * " have the same meanings as in formula (A1-1) and d is an integer of 1 to 10)

A group represented by each of R < 1 >

The group represented by the formula (A1-2) is preferably a group represented by the following formula:

(Wherein R ³ and "*" have the same meanings as in formula (A1-2), respectively)

And a group represented by each of R < 1 >

The polyorganosiloxane (A) in the present invention preferably has a structure represented by the above formula (A1) in an amount of 0.2 to 6 mmol / g, more preferably 0.3 to 5 mmol / g.

The weight average molecular weight of the polyorganosiloxane (A) in the present invention, as measured by gel permeation chromatography, in terms of polystyrene is preferably 1,000 to 500,000, and more preferably 2,000 to 200,000.

As described above, the polyorganosiloxane (A) may be produced by any method as long as it has a structure represented by the formula (A1) in the above-mentioned range, but for example,

A mixture of silane compounds containing an epoxy group and a silane compound having a hydrolyzable group (hereinafter referred to as " silane compound (1) ") is preferably hydrolyzed and condensed in the presence of an organic solvent, Organosiloxane (hereinafter referred to as " precursor of polyorganosiloxane (A) ") is synthesized first, and then

(Hereinafter referred to as " compound (A1) ") having the structure represented by the formula (A1) and a group capable of reacting with the epoxy group. At this time, a compound having no group represented by the formula (A1) and having a group capable of reacting with an epoxy group (hereinafter referred to as "other reactive compound") may be used together with the compound (A1).

Examples of the silane compound (1) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidylsilane, 3-glycidyloxypropyldimethylethoxysilane, 2- 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldi 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxide (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyltriethoxysilane, and the like, and at least one selected from these can be used.

The silane compound used for synthesizing the precursor of the polyorganosiloxane (A) may be composed solely of the silane compound (1) as described above, or may be a silane compound other than the silane compound (1) Quot; silane compound (2) ").

Examples of the silane compound (2) usable herein include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- N-propoxysilane, tri-n-butoxysilane, tri-n-butoxysilane, tri-n-butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, n-propoxysilane, fluorotri-n-propoxysilane, fluorotri-n-butoxy silane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri- Silane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n Butoxy silane, methyl tri-sec-butoxysilane, 2- (trifluoromethyl) ethyl trichloro (Trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- Butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltri- (Perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (Perfluoro-n-hexyl) ethyl tri-n-hexyl) ethyl tri-n-propoxysilane, 2- (perfluoro- N-butoxy silane, 2- (perfluoro-n-hexyl) ethyl tri-sec-butoxysilane,

2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro- Octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro- ) Ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, Hydroxymethyl tri-n-propoxysilane, hydroxymethyl tri-n-butoxysilane, hydroxymethyl tri-sec-butoxysilane, 3- ( (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- , 3- (meth) acrylic (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3- Mercaptopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, aryltrichlorosilane, N-propoxysilane, aryltriethoxysilane, aryltri-n-propoxysilane, aryltri-i-propoxysilane, aryltri-n-butoxysilane N-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-propoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltri- Butoxysilane, methyldi-i-propoxysilane, methyldi-i-propoxysilane, methyldi-n-propoxysilane, Butoxysilane, dimethyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, Butoxy silane, dimethyl di-sec-butoxy silane,

(Perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, N-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] (Methyl) [2- (perfluoro-n-octyl) ethyl] di-i-propoxysilane, Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3- mercaptopropyl) dimethoxysilane, Propoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, Diethoxy silane, (methyl) (vinyl) di-n-propoxy (Methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, di (vinyl) di-n-butoxysilane, Divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane , Diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyl Di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxy Propoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (Methyl) diphenylsilane, (ethoxy) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) Besides the silane compound having one silicon atom such as silane,

X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, K- X-22-170BX, X-22-170D, X-22-170DX, X-22-170B, X-21-5846, X- X-22-176D, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- KR-200, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR- KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (all manufactured by Shin-Etsu Chemical Co., Ltd.);

Glass resin (manufactured by Showa Denko K.K.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning);

FZ3711, FZ3722 (manufactured by Nippon Unicar Co., Ltd.);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931 and XMS-5025 (all manufactured by Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (all manufactured by Mitsubishi Chemical Corporation);

Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.);

GR100, GR650, GR908 and GR950 (all manufactured by Showa Denko K.K.).

Of these silane compounds (2), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, aryltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferable.

The precursor of the polyorganosiloxane (A) preferably used in the present invention has an epoxy equivalent of 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol, and particularly preferably 150 to 300 g / desirable. Therefore, in synthesizing the precursor of the polyorganosiloxane (A), the use ratio of the silane compound (1) and the silane compound (2) is adjusted so that the epoxy equivalence of the obtained polyorganosiloxane is in the above range, . In synthesizing the precursor of the polyorganosiloxane (A) used in the present invention, it is preferable that only the silane compound (1) is used and no other silane compound is used.

Examples of the organic solvent that can be used for synthesizing the precursor of the polyorganosiloxane (A) include hydrocarbon, ketone, ester, ether, alcohol and the like.

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

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

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

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

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

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

The amount of the organic solvent to be used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound.

The amount of water used when preparing the precursor of the polyorganosiloxane (A) is preferably 0.5 to 100 times by mole, more preferably 1 to 30 times by mole based on the total amount of the silane compound.

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

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

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

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

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

Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As the catalyst for producing the precursor of the polyorganosiloxane (A), an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reaction such as ring opening of an epoxy group, It is preferable that stability is improved. Further, the liquid crystal aligning agent of the present invention containing the polyorganosiloxane (A) prepared from the precursor synthesized by using an alkali metal compound or an organic base as a catalyst is very suitable because of its extremely excellent storage stability. The reason is that the formation of a three-dimensional structure is promoted, and it is inferred that a polyorganosiloxane having a small content of silanol groups is obtained. That is, since the polyorganosiloxane (A) has a small content of the silanol group, the condensation reaction between the silanol groups is suppressed and the condensation reaction with the polymer (B) is suppressed. As a result, .

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used is appropriately set depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, but is preferably 0.01 to 3 times by mol, more preferably 0.05 to 1 It is a boat mall.

The hydrolysis or hydrolytic condensation reaction in the production of the precursor of the polyorganosiloxane (A) is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, For example, by heating with an oil bath or the like.

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

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, it is preferable that the cleaning is carried out by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt% or the like. The washing is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the intended polyorganosiloxane (A ) Can be obtained.

The weight average molecular weight (Mw) of the precursor of the polyorganosiloxane (A) in terms of polystyrene measured by gel permeation chromatography is preferably 1,000 to 1,000,000, more preferably 1,500 to 300,000.

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

The compound (A1) used in the present invention is a compound having a structure represented by the formula (A1) and a group capable of reacting with an epoxy group. The compound (A1) having the structure represented by the formula (A1-1) is preferably a compound represented by the following formulas (A1-1C) and (A1-2C):

(R ¹ , R ¹ , R ² , X ¹ , X ² , a and b in the formula (A1-1C)

R, R ³ , R ⁴ , X ³ , X ⁴ , a and c in the formula (A1-2C) have the same meanings as those in the formula (A1-1) or (A1-2), respectively;

X ⁵ in the formula (A1-1C) is a single bond, an oxygen atom, a sulfur atom, a methylene group, an alkylene group having 2 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or a divalent aromatic group,

When X ⁵ is a monocyclic bond, e is 1 and R ⁵ is a hydrogen atom,

When X ⁵ is a methylene group, an alkylene group, an alkenylene group or a bivalent aromatic group, e is 0 or 1, and R ⁵ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR Or an alkyl group having 1 to 6 carbon atoms), -CH = CH ₂ or -SO ₂ Cl;

R ⁶ in the formula (A1-2C) is a bivalent aromatic group, a divalent heterocyclic group or a divalent fused ring group, and X ⁶ is an oxygen atom, -COO- ⁺ or -OCO- ⁺ Quot; + " is combined with R < ⁶ >),

f is an integer of 0 to 3,

R ⁷ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (however, the R is an alkyl group for a hydrogen atom or a carbon number of 1~6), -CH = CH ₂ or -SO ₂ Cl, X ⁷ is a single _{bond, -OCO- (CH 2) i -} + or ^{_{-O- (CH 2) j - +}} ( However, the i and j are each an integer of 0 to 10, the coupling hand tagged "+" R ⁷ and Lt; / RTI >

≪ / RTI >

The compound represented by the formula (A1-1C) is preferably a compound wherein X ⁵ is a single bond and R ⁵ is a carboxyl group in the formula (A1-1C)

X ⁵ is a methylene group, an alkylene group or a bivalent aromatic group, and R ⁵ is a carboxyl group;

As the compound represented by the formula (A1-2C), a compound in which R ⁷ in the formula (A1-2C) is a carboxyl group is preferable. Such a compound (A1) having a carboxyl group is hereinafter referred to as " carbonic acid (A1) ".

More preferable examples of such a carboxylic acid (A1) include compounds represented by the above formula (A1-1C), for example, the following formulas:

(Wherein R < ¹ > is the same as those in formula (A1-1), and d is an integer of 1 to 10)

And the like;

As the compound represented by the formula (A1-2), a compound represented by the following formula:

(Wherein R ³ has the same meaning as in formula (A1-2), respectively)

And the like.

The other reactive compound is preferably a compound having a carboxyl group as a group capable of reacting with an epoxy group,

(Hereinafter referred to as "other carbonic acid (1)") having a pretilt angular expression structure,

(Hereinafter referred to as " other carbonic acid (2) ") having at least one structure out of a structure capable of generating a radical by irradiation with light and a structure having a photosensitizing function, and

Other carbonic acid other than the above (hereinafter referred to as "other carbonic acid (3)")

Etc., and at least one selected from the group consisting of these can be used.

The pretilt angular expression structure in the other carbonic acid (1) includes, for example, an alkyl group or an alkoxyl group having 8 to 20 carbon atoms or a fluoroalkyl group having 1 to 21 carbon atoms or a fluoroalkoxyl group or an alicyclic group And a monovalent organic group having 3 to 40 carbon atoms.

Examples of the other carbonic acid (1) having such a structure include the following formulas (C-1) to (C-4):

(H in the formula (C-1) is an integer of 1 to 3, and i is an integer of 3 to 18;

J in the formula (C-2) is an integer of 5 to 20;

K in the formula (C-3) is an integer of 1 to 3, and m is an integer of 0 to 18; Also

N in the formula (C-4) is an integer of 1 to 18)

And the like. Among them, the compound represented by each of the above-mentioned formulas (C-2), (C-3) and (C-4), more preferably the compound represented by the above formula (C-2) 4- (n-pentyl) benzoic acid, 4- (n-pentyl) benzoic acid, 4- n-decyl benzoic acid, 4- (n-dodecyl) benzoic acid, 4- (n-octadecyl) benzoic acid and the like;

Examples of the compound represented by the above formula (C-3) include compounds represented by the following formulas (C-3-1) to (C-3-3):

And the like;

Examples of the compound represented by the above formula (C-4) include 4- (n-butoxy) benzoic acid, 4- (n-pentyloxy) benzoic acid, 4- (N-decyloxy) benzoic acid, 4- (n-dodecyloxy) benzoic acid, 4- (n-octyloxy) (n-octadecyloxy) benzoic acid, and the like, and at least one selected from them may be used.

The photo-sensitization function of the other carbonic acid (2) refers to a function of rapidly transiting into a triplet excited state due to rapid cross-linking after becoming a singlet excited state by irradiation of light, Refers to a function of colliding with another molecule in the anti-excited state to change the other to an excited state and returning to the base state by itself. This photo-sensitization function may coexist with a function of generating a radical by light irradiation.

Examples of the structure of at least one of the structure for generating a radical by light irradiation and the structure having a photosensitizing function include a benzophenone structure, a 9,10-dioxodihydroanthracene structure, a 1,3-dinitrobenzene structure Dioxocyclohexa-2,5-diene structure, that is, the following formulas (1) to (4):

, And at least one structure selected from these can be used. Examples of the other carbonic acid (2) having such a structure include 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 4- Benzoic acid, 3- (2-hydroxybenzoyl) benzoic acid, 4- (4-methylbenzoyl) Benzoyl-phenoxy) propionic acid, 9,10-dioxodihydroanthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3- (9,10-dioxo-9,10-dihydroanthracene 2-yl) propionic acid, 3,5-dinitrobenzoic acid, 4- [4- (4-fluorobenzyloxy) Methyl-3,5-dinitrobenzoic acid, 3- (3,5-dinitrophenoxy) propionic acid and 2-methyl-3,5-dinitrobenzoic acid.

Examples of the other carbonic acid (3) include formic acid, acetic acid, propionic acid and benzoic acid.

The use ratio of the carboxylic acid (A1) used in the production of the polyorganosiloxane (A) in the present invention is 0.001 to 1 mole relative to 1 mole of the epoxy group of the precursor of the polyorganosiloxane (A) More preferably 0.1 to 1 mol, and still more preferably 0.2 to 0.9 mol.

The ratio of the other carbonic acid (1) used in the production of the polyorganosiloxane (A) in the present invention is preferably 0.5 mol or less with respect to 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A) , And more preferably 0.01 to 0.3 mol.

The ratio of the other carbonic acid (2) used in the production of the polyorganosiloxane (A) in the present invention is preferably 0.3 mol or less with respect to 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A) , More preferably from 0.0001 to 0.1 mol.

The ratio of the other carbonic acid (3) used in the production of the polyorganosiloxane (A) in the present invention is 0.3 mol or less relative to 1 mol of the epoxy group of the precursor of the polyorganosiloxane (A) , More preferably from 0.0001 to 0.2 mol.

When the polyorganosiloxane (A) of the present invention is used in combination with other carbonic acid in addition to the carbonic acid (A1), the carbonic acid (A1) is used in an amount of 10 mol% or more based on the total amount of the carbonic acid . When other carbonic acid (2) is used, the amount of the other carbonic acid (2) is preferably 30 mol% or less, more preferably 15 mol% or less based on the total amount of all carbonic acid .

When the polyorganosiloxane (A) according to the present invention is produced, the total use ratio of the carbonic acid is 0.01 to 1 mole relative to 1 mole of the epoxy group contained in the precursor of the polyorganosiloxane (A) And more preferably 0.1 to 0.75 mol.

The reaction of the precursor of the polyorganosiloxane (A) with the above-described carboxylic acid can be carried out in the presence of a suitable catalyst, preferably in an appropriate organic solvent.

As the catalyst to be used herein, an organic base can be used, and a known compound can be used as a so-called curing accelerator for accelerating the reaction between the epoxy compound and the carboxylic acid.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

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

And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; And quaternary organic amines such as tetramethylammonium hydroxide are preferable, and at least one selected from the above can be used.

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

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

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphate;

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

1,8-diazabicyclo [5.4.0] undecene-7, a diazabicyclicalkene such as an organic acid salt thereof;

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

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

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as dicyandiamide or an amine addition type accelerator such as an adduct of an amine and an epoxy resin;

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

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

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

The amount of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the precursor of the polyorganosiloxane (A).

Examples of the organic solvent used in the reaction of the precursor of the polyorganosiloxane (A) with the carboxylic acid include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds and alcohol compounds. Of these, ether compounds, ester compounds and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. The solvent is used in an amount such that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1 wt% or more, more preferably 5 to 50 wt% .

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

The preferred polyorganosiloxane (A) in the present invention employs a polyorganosiloxane having an epoxy group as a raw material and introduces the structure represented by the formula (A1) by the ring-opening portion of the epoxy. This manufacturing method is simple. Furthermore, it is a particularly suitable method in that the introduction rate of the structure represented by the formula (A1) can be increased.

≪ Polyamic acid (B) >

In the liquid crystal aligning agent of the present invention, the polyamic acid (B)

Tetracarboxylic acid dianhydride and

(b2) a diamine having a carboxyl group (hereinafter referred to as "diamine (b2)")

≪ / RTI >

. ≪ / RTI > The diamine preferably further comprises

(b1) an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected, or a diamine having a group having a steroid structure.

Examples of the tetracarboxylic acid dianhydrides used herein include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 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 anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetralone, and the like;

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like,

Tetracarboxylic acid dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (B), those containing an alicyclic tetracarboxylic acid dianhydride are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid 2-anhydride or 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (B) include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, Is preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more, relative to tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or 1,2,3,4 -Cyclobutane tetracarboxylic acid dianhydride.

The diamine (b1) is an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected, or a diamine having a group having a steroid structure. As the diamine (b1), a diamine having a structure in which two or more 6-membered rings are connected or a group having a steroid structure is further substituted with an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, Or an alkoxyl group having 4 to 20 carbon atoms. Examples of the group having a steroid structure include a cholestan-3-yl group, a cholestan-5-en-3-yl group, a cholestan- 3-yl group, a lanostan-3-yl group and the like.

Examples of the diamine (b1) in the present invention include 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) Methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, the following formula (b1-1):

(Formula (b1-1), X is a single bond, methylene group, alkylene group having 2 or ^{3 * -O-, * -COO-, *} -OCO-, * -X'-R "-, * -R "-X'- or ^{* -X'-R" -X '-} ( stage, X' ⁺ are each -O-, -COO- or ^{+ +} -OCO- (However, the "+" is a bond attached this (3-1-1)), R "is an alkylene group having 2 or 3 carbon atoms, and a bond with " * " is bonded to a diaminophenyl group) n1 is an integer of 0 to 2, n2 is 0 or 1, and when n1 + n2 is 2 or more, R 'is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, 0 or 1, R 'is a group having a steroid structure, an alkyl group having 4 to 20 carbon atoms, or a fluoroalkyl group having 4 to 20 carbon atoms)

And the like. The alkyl group and the fluoroalkyl group in the above formula (b1-1) are preferably each straight-chain.

The diamine (b1) in the present invention is preferably a compound represented by the above formula (b1-1), and specific examples thereof include n-dodecaneoxy-2,4-diaminobenzene, n-tetra Decanoxy-2,4-diaminobenzene, n-pentadecanoxy-2,4-diaminobenzene, n-hexadecanoxy-2,4-diaminobenzene, n- octadecanoxy- Diaminobenzene, n-dodecaneoxy-2,5-diaminobenzene, n-tetradecanoxy-2,5-diaminobenzene, n-pentadecaneoxy- 2,5-diaminobenzene, n-hexadecanoxy Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, Stearyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5 -Diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis ) Stan Collet, formula (b1-1-1) ~ (b1-1-7):

≪ / RTI >

The liquid crystal aligning agent containing a polyamic acid (B) synthesized using a diamine containing the diamine (b1) and the polyimide (B) obtained by dehydration cyclization of the polyamic acid is particularly preferable as a VA liquid crystal display element It is very suitable for forming a liquid crystal alignment film.

The diamine (b2) is a diamine having a carboxyl group. Preferable examples of such diamine (b2) include the following diamines (b2-1):

(In the formula (b2-1), y is an integer of 0 to 2;

x is an integer of 0 to 4, provided that when there are a plurality of x, each x may be the same or different from each other;

R ^I is a single bond, a methylene group, an alkylene group or a cyclohexylene group having 2 to 6 carbon atoms, provided that the alkylene group may be interrupted by an ether bond or an ester bond;

X ^I represents a single bond, methylene group, methylene group, fluoroalkyl, alkylene group having 2 to 4 carbon atoms, fluoroalkyl group having 2 to 4 carbon atoms, an oxygen atom, a carbonyl ^{group, * -COO-, * -OCO-, *} - NH-, ^* -CONH-, -NHCO- ^* (in the above, "*", then this indicates that this combination hand attached toward the left of the formula (b2-1)), or the following formula (X ^I -1):

(Formula (X ^I -1) of, R ^II is interrupted by a single bond, a methylene group, an alkylene group or a cyclohexylene group having a carbon number of 2 to 6, with the proviso that the ether linkage or ester bond during said alkylene group It may be good;

R ^III is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group -R ^IV COOH (wherein R ^IV is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms or a cyclohexylene group, And the group may be interrupted by an ether bond or an ester bond in the middle)

Is a group represented by

The total number of carboxyl groups in the formula (b2-1) is an integer of 1 to 4)

Lt; / RTI >

Each of R ^I in the formula (b2-1) is preferably a methylene group or an alkylene group having 2 to 5 carbon atoms.

The compound represented by the formula (b2-1) is preferably a compound in which at least one of x in the formula (b2-1) is 1 and the group X ^I is not a group represented by the formula (XI-1)

Is preferably a compound wherein all of x in the formula (b2-1) is 0 and the group X ^I is a group represented by the formula (XI-1).

The compound represented by the above formula (b2-1) is more preferably a compound represented by any one of the following formulas (b2-1-1) to (b2-1-5):

(In the formula, X is ^I, each of the formula (b2-1) as defined and X ^I in a;

R ^III is an alkyl group having 1 to 6 carbon atoms;

x is an integer from 1 to 4;

z is an integer of 1 to 5,

d is an integer of 1 to 4)

≪ / RTI > It is preferable that x and d in the formulas (b2-1-1), (b2-1-2) and (b2-1-5) are 1, respectively.

The compound represented by the formula (b2-1) is preferably a compound represented by the formula (b2-1-1), (b2-1-2) or (b2-1-5) For example, 3,5-diaminobenzoic acid, the following formulas (b2-1-2-1) and (b2-1-5-1):

≪ / RTI >

The diamine in the present invention may be composed solely of diamines (1) and diamines (2) as described above, or may contain diamines other than diamines (1) and diamines (2) Quot;).

Examples of the diamine (3) usable herein include aliphatic diamines other than diamines (1) and diamines (2), alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) 4-aminophenyl) -piperazine, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) ) Cyclohexyl-3, 5-diaminobenzoate, and the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like,

Diamines described in Japanese Patent Application No. 2009-157556, diamines (1) and diamines (2) can be used.

The diamine used for synthesizing the polyamic acid (B) preferably contains 10 mol% or more, more preferably 30 mol% to 70 mol% of the diamine (1) based on the total diamine, More preferably 35 to 60 mol%;

The diamine (2) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% to 70 mol%, and still more preferably 40 mol% to 65 mol% with respect to the total diamine. The diamine used for synthesizing the polyamic acid (B) may contain the diamine (3) in an amount of 80 mol% or less based on the total diamine, and may be contained in an amount of 5 to 40 mol% .

When the diamine used for synthesizing the polyamic acid (B) contains the diamine (1) in the above-mentioned range, the obtained liquid crystal aligning agent exhibits good burning resistance and good pretilt angle expression It is possible to form a liquid crystal alignment film compatible with the liquid crystal alignment film. Further, by including the diamine (2) in the above-mentioned range, the good printability of the obtained liquid crystal aligning agent and excellent electrical characteristics (particularly voltage holding ratio) of the liquid crystal alignment layer to be formed are excellent.

The polyamic acid (B) can be synthesized by reacting the aforementioned tetracarboxylic acid dianhydride with a diamine.

The proportion of the tetracarboxylic acid dianhydride and the diamine used in the synthesis reaction of the polyamic acid (B) is preferably in the range of 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group of the diamine , More preferably 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent at a temperature of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours Time is done.

Examples of the organic solvent include aprotic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Butyrolactone, tetramethylurea, hexamethylphosphoric triamide and the like;

As the phenol derivative, for example, m-cresol, xylenol, halogenated phenol and the like;

As the alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;

As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate and the like;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetraethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Hydrofuran and the like;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutylate, and diisopentyl ether.

Among these organic solvents, at least one selected from the group consisting of an aprotic polar solvent and a group consisting of phenol and derivatives thereof (first group of organic solvents), or at least one selected from organic solvents of the first group and an alcohol , A ketone, an ester, an ether, a halogen hydrocarbons and a hydrocarbon (second group of organic solvents). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group And more preferably 30% by weight or less.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

Thus, a reaction solution obtained by dissolving the polyamic acid (B) is obtained.

This reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided after preparation of the liquid crystal aligning agent after isolation of the polyamic acid (B) contained in the reaction solution, or purified polyamic acid (B) May be provided later for preparation of the liquid crystal aligning agent. When the polyamic acid (B) is subjected to dehydration ring closure to form polyimide (B), the reaction solution may be directly supplied to the dehydration ring-closing reaction, or the polyamic acid (B) contained in the reaction solution may be isolated, Or may be provided to the dehydration ring-closing reaction after the isolated polyamic acid (B) is purified. The polyamic acid (B) can be isolated and purified by a known method.

≪ Polyimide (B) >

The polyimide (B) in the present invention can be obtained by subjecting the polyamic acid (B) synthesized as described above to dehydration cyclization and imidization.

The polyimide (B) in the present invention may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structure possessed by the polyamic acid (B) which is a precursor thereof. The polyimide (B) Or a partially imide cargo in which an imide ring structure coexists. The polyimide (B) in the present invention preferably has an imidization ratio of 10 to 90%, more preferably 20 to 80%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring-closure of the polyamic acid (B) is preferably carried out by heating the polyamic acid (B), or by dissolving the polyamic acid (B) in an organic solvent, adding a dehydrating agent and a dehydrating ring- And heating it in accordance with the above-mentioned method. Of these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution of the polyamic acid (B), an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. 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 the polyamic acid (B). The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

Thus, a reaction solution containing the polyimide (B) is obtained. This reaction solution may be supplied directly to the preparation of a liquid crystal aligning agent or may be provided in the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. After separating the polyimide (B) May be added to the preparation of the liquid crystal aligning agent after the purified polyimide (B) is purified. These purification operations can be carried out according to a known method.

<Other components>

The liquid crystal aligning agent of the present invention contains at least one kind of polymer selected from the group consisting of the polyorganosiloxane (A) and the polyamic acid (B) and the polyimide (B), but the effect of the present invention Other components may optionally be included as long as they do not impair the properties of the composition. Examples of other components that can be used herein include polymers other than the polyorganosiloxane (A), the polyamic acid (B) and the polyimide (B) (hereinafter referred to as "other polymer"), a curing agent, A compound having at least one epoxy group in the molecule (hereinafter referred to as &quot; epoxy compound &quot;), a functional silane compound, a surfactant, and a photosensitizer.

[Other Polymers]

These other polymers can be used to further improve the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. Examples of such other polymers include polyorganosiloxanes other than polyorganosiloxane (A) (hereinafter referred to as "other organosiloxane"), polyamines other than polyamic acid (B) (Hereinafter referred to as &quot; other polyimide &quot;), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly Maleimide) derivatives, and poly (meth) acrylates. Of these, other organosiloxanes, other polyamic acids, and other polyimides are preferable, and at least one selected from these may be used.

The other polyorganosiloxane can be obtained by hydrolysis and condensation of at least one member selected from the group consisting of silane compounds (1) and (2). The precursor of the polyorganosiloxane (A) may also be used as other polyorganosiloxane as referred to herein. The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the other polyorganosiloxane in the present invention is preferably 500 to 100,000, more preferably 500 to 10,000.

Those skilled in the art will recognize that the synthesis reaction of other polyorganosiloxanes as well as isolation and purification can be performed in accordance with the examples of the polyorganosiloxane (A).

Other polyamic acids,

Tetracarboxylic acid dianhydride,

A diamine selected from the group consisting of the diamines (b1) and (b3)

, Or

Tetracarboxylic acid dianhydride,

At least one diamine selected from the group consisting of the diamines (b2) and (b3)

. &Lt; / RTI &gt; Other polyimides can be obtained by dehydrating and ring closure of other polyamic acids as described above to imidize them. The imidization ratio of the other polyimide is preferably 30% or more, more preferably 40 to 80%.

Other polyamic acids and other polyimides may be synthesized, and their isolation and purification may be carried out in accordance with examples of polyamic acid (B) or polyimide (B).

[Curing agent and curing catalyst, also curing accelerator]

The curing agent and the curing catalyst may be contained in the liquid crystal aligning agent of the present invention for the purpose of strengthening the crosslinking reaction of the polyorganosiloxane (A), and the curing accelerator may accelerate the curing reaction May be contained in the liquid crystal aligning agent of the present invention for the purpose.

As the curing agent, a curing agent generally used for curing a curable composition containing an epoxy group or a compound having an epoxy group can be used. Examples of the curing agent include a polyvalent amine, a polyvalent carboxylic acid anhydride, For example.

Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides.

Examples of the cyclohexanetricarboxylic acid anhydride include 5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride and the like. Examples of the acid anhydride include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride,

(Wherein m is an integer of 1 to 20)

And tetracarboxylic acid dianhydrides generally used in the synthesis of polyamic acids, alicyclic compounds having conjugated double bonds such as alpha -terpinene and alo cymene, and diols Alder with ally maleic anhydride ) Reaction products and hydrogenated products thereof.

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

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

A quaternary compound;

Quaternary amine compounds;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or an organic acid salt thereof;

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

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

Amine-type accelerators such as dicyandiamide, adducts of amines and epoxy resins, and the like;

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

Amine salt type latent curing accelerator;

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

[Epoxy Compound]

The epoxy compound is a compound having at least one epoxy group in the molecule, but excludes those corresponding to the polyorganosiloxane (A) or other polyorganosiloxane.

Such an epoxy compound can be contained in the liquid crystal aligning agent of the present invention from the viewpoint of further improving adhesion to the substrate surface of the liquid crystal alignment film to be formed.

Examples of such epoxy compounds 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, Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- Di-aminomethylcyclohexane, and the like.

When the liquid crystal aligning agent of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing a crosslinking reaction thereof.

[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- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. And a reaction product of a tetracarboxylic acid dianhydride and a silane compound having an amino group as described in Patent Document 10 (Japanese Unexamined Patent Publication (Kokai) No. 63-291922).

[Surfactants]

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

[Photosensitizer]

Examples of the photosensitizer include duren, benzonitrile, butyrophenone, propiophenone, acetophenone, xanthone, 4-methoxyacetophenone, 3-methoxyacetophenone, anthrone, benzaldehyde, 4,4 ' -Dimethoxybenzophenone, benzophenone, fluorene, triphenylene, biphenyl, thioxanthone, anthraquinone, 4,4'-bis (diethylamino) benzophenone, phenanthrene, naphthalene, 4-phenylacetophenone , 4-phenylbenzophenone, 2-iodonaphthalene, acenaphthene, 2-naphthonitrile, 1-iodonaphthalene, 1-naphthonitrile, chrysene, coronene, benzyl, fluoranthene, pyrene, -Benzoanthracene, acridine, anthracene, tetracene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, 9-cyananoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetra And cyano anthracene.

&Lt; Use ratio of each component >

The proportion of each component in the liquid crystal aligning agent of the present invention is as follows.

When the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of other polyamic acids and other polyimides, the proportion of these other polymers to be used is preferably such that the sum of the polyamic acid and the polyimide Is preferably 90% by weight or less, more preferably 70% by weight or less based on the total amount of the polyamic acid (B) and polyimide (B), and other polyamic acids and other polyimides which may optionally be used Is more preferable.

The liquid crystal aligning agent of the present invention is a polymer,

The polyorganosiloxanes (A) and

At least one kind of polymer selected from the group consisting of polyamic acid (B) and polyimide (B) and

But the use ratio thereof is not particularly limited,

The proportion of the polyorganosiloxane (A) to 100 parts by weight of the total of the polyamic acid and the polyimide is preferably 0.1 to 100 parts by weight, more preferably 1 to 5 parts by weight, still more preferably 5 to 15 parts by weight . When the ratio is used in this range, it is possible to realize an appropriate pretilt angle manifestation while maintaining good applicability and printability of the obtained liquid crystal aligning agent, which is preferable.

When the liquid crystal aligning agent of the present invention contains other polyorganosiloxane, the proportion thereof is preferably 100 parts by weight or less, more preferably 50 parts by weight or less based on 100 parts by weight of the total of polyamic acid and polyimide By weight, more preferably 20 parts by weight or less.

When the liquid crystal aligning agent of the present invention contains a curing agent, the use ratio thereof is preferably 100 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

When the liquid crystal aligning agent of the present invention contains a curing catalyst, the use ratio thereof is preferably 2 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

When the liquid crystal aligning agent of the present invention contains a curing accelerator, the use ratio thereof is preferably 10 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

When the liquid crystal aligning agent of the present invention contains an epoxy compound, the use ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight per 100 parts by weight of the sum of polyamic acid and polyimide Wealth. When a base catalyst is used together with the epoxy compound, the use ratio thereof is preferably 10 parts by weight or less, more preferably 0 to 2 parts by weight, based on 100 parts by weight of the epoxy compound.

When the liquid crystal aligning agent of the present invention contains a functional silane compound, the use ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the total of polyamic acid and polyimide Or less.

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

When the liquid crystal aligning agent of the present invention contains a photosensitizer, the use ratio thereof is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the polyorganosiloxane (A) to be.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains such a polymer and optionally other components, and is preferably prepared as a solution composition dissolved in a suitable organic solvent.

Examples of the organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention include at least one kind of polymer selected from the group consisting of polyorganosiloxane (A), polyamic acid (B) and polyimide (B) It is preferable that the other components to be used are dissolved and not reacted with these components. Examples of the organic solvent which can be preferably used in the liquid crystal aligning agent of the present invention include the organic solvents exemplified above which are used for the synthesis of the polyorganosiloxane (A), the polyamic acid (B) and the polyimide (B) And at least one selected from these can be used.

The preferred solvent used in the preparation of the liquid crystal aligning agent of the present invention is one of the above organic solvents or a combination of two or more of the organic solvents described above and is preferably a liquid crystal aligning agent And the surface tension of the liquid crystal aligning agent is in the range of 25 to 45 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., By weight. The liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film that becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film . On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased, and coating properties are sometimes insufficient. A particularly preferable range of the solid concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the range of 1.5 to 4.5 wt% is particularly preferable. In the case of the printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. 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 for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, more preferably 10 ° C to 60 ° C.

&Lt; Method of forming liquid crystal alignment film &

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

As a method of forming a liquid crystal alignment film, there is a method of applying a liquid crystal alignment film of the present invention on a substrate to form a coating film, and then irradiating the coated film with polarized or unpolarized radiation to give more liquid crystal alignment capability .

First, the liquid crystal aligning agent of the present invention is applied to the transparent electroconductive film side of the substrate on which the patterned transparent electroconductive film is formed by a suitable application method such as a roll coater method, a spinner method, a printing method, or an ink jet method. Then, the coated surface is preheated (prebaked) and then baked (post baked) to form a coated film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 占 폚, and the postbaking condition is preferably 120 to 300 占 폚, more preferably 150 to 250 占 폚, preferably 5 to 200 minutes, More preferably 10 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

As the substrate, for example, a transparent substrate made of plastic such as glass such as float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and cyclic olefin resin can be used.

As the transparent conductive film, a NESA (registered trademark) film made of SnO ₂ , an ITO film made of In ₂ O ₃ -SnO ₂ , or the like can be used. For patterning these transparent conductive films, a known method 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 coating film.

Subsequently, the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized light to impart liquid crystal aligning ability. Here, as the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. In the case where the used radiation is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, and more preferably 10 to 3,000 J / m 2. Further, in the case of imparting the liquid crystal aligning ability to the coating film formed by the conventionally known liquid crystal aligning agent by the photo alignment method, a radiation dose of 10,000 J / m 2 or more was required. However, when the liquid crystal aligning agent of the present invention is used, a good liquid crystal aligning ability can be imparted even when the irradiation dose is 3,000 J / m 2 or less and 1,000 J / m 2 or less at the time of the photo alignment method, .

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element of the present invention comprises a liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention. The liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention is preferable because it can maximally exhibit its advantageous effect when applied to a vertical alignment type liquid crystal display device.

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

Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is arranged between the two substrates to manufacture a liquid crystal cell. In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

In the first method, two substrates are opposed to each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant, A liquid crystal is injected and filled in a cell gap defined by the liquid crystal cell, and then the injection hole is sealed. Thus, a liquid crystal cell can be manufactured.

The second method is a so-called ODF (One Drop Fill) method. For example, an ultraviolet curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed and the liquid crystal is dropped on the liquid crystal alignment film, The liquid crystal cell can be manufactured by bonding the substrate and then curing the sealant by irradiating ultraviolet rays to the entire surface of the substrate.

In either case, it is preferable that the liquid crystal cell is heated to a temperature at which the used liquid crystal has an isotropic phase, and then the liquid crystal cell is gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film is vertically aligned, a cell is constituted so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, and the polarization direction of the polarizing plate is 45 degrees So that a liquid crystal display element having a vertically aligned liquid crystal cell can be obtained.

As the sealant, 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 preferably used.

In the case of the vertical alignment type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a sip base liquid crystal, Based liquid crystal, a phenylcyclohexane-based liquid crystal, and the like.

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

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

[Example]

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

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

Column: TSKgelGRCXLII, manufactured by Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

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

The solution viscosity of the polymer solution is a value measured at 25 占 폚 using an E-type viscometer for a polymer solution (solvent: N-methyl-2-pyrrolidone) having a polymer concentration of 20% by weight specified in each synthesis example.

The imidization rate of the polyimide was measured by putting the polyimide solution obtained in each synthesis example into pure water, sufficiently drying the resulting precipitate under reduced pressure at room temperature, dissolving the precipitate in heavy hydrated dimethylsulfoxide, , And was determined from the ¹ H-NMR spectrum measured at room temperature by the following formula (1).

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

(In the formula (1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton,

and? is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamic acid)

In the following, the synthesis of the raw material compound and the polymer was repeated as necessary with the following synthesis scales, thereby securing an amount of the compound to be used for the subsequent synthesis.

<Synthesis of polyorganosiloxane having epoxy group (precursor of polyorganosiloxane (A))>

Synthesis Example E-1

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

¹ H-NMR analysis was performed on this polyorganosiloxane (EPS-1), and a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity, and a side reaction of the epoxy group It was confirmed not to happen.

The polyorganosiloxane (EPS-1) had a weight average molecular weight (Mw) of 2,200 and an epoxy equivalent of 186 g / mol.

&Lt; Synthesis of carbonic acid (A1) >

In the following synthesis examples, the following formulas (A-1) to (A-8)

Were synthesized. Hereinafter, the compound represented by each of the above formulas (A-1) to (A-8) is referred to as "compound (A-1)" to "compound (A-8)".

Synthesis Example A-1

12 g of n-decylsuccinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were placed in a 200 mL eggplant-shaped flask equipped with a reflux tube, and the reaction was carried out under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the obtained organic layer was washed with water, dried over magnesium sulfate, and then purified by column chromatography (filler: silica gel, developing solvent: chloroform / methanol = 8/2 And recrystallization was performed from a mixed solvent of ethanol and tetrahydrofuran to obtain 10 g of white crystals (purity: 98.0%) of the compound (A-1).

Synthesis Example A-2

82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate and 400 mL of N-methyl-2-pyrrolidone were placed in a 1 L eggplant-shaped flask and stirred at room temperature for 1 hour. Then, 212 g of 1-bromooctane was added, Lt; / RTI &gt; for 5 hours. Thereafter, the solvent was distilled off under reduced pressure. 48 g of sodium hydroxide and 400 ml of water were added thereto, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain 80 g of white crystals of the compound (A-2).

Synthesis Example A-3

107 g of 4-bromo cinnamic acid was refluxed in 83 g of thionyl chloride for 4 hours to obtain a red transparent solution. Subsequently, the unreacted thionyl chloride was distilled off, and the residue was recrystallized from toluene. The obtained crystals were washed with n-hexane to obtain 85 g of white crystals of 4-bromosuccinic acid chloride.

Next, 25.0 g (0.147 mol) of 4-amylcyclohexanol was dissolved in 25 mL of pyridine. While keeping the temperature of the solution at about 3 占 폚, 43.3 g (0.176 mol) of the 4-bromo cinnamic chloride obtained above was suspended in 350 ml of pyridine, and the solution was dropped thereon and reacted for 3 hours. The resulting reaction mixture (suspension) was put into 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered, washed with water and dried to obtain a crude product of 4-n-pentylcyclohexyl ester of 4-bromocinnamic acid 50 g.

To a mixture of 50 g of the crude 4-n-pentylcyclohexyl ester of 4-bromocinnamic acid thus obtained, 0.28 g of palladium acetate and 1.52 g of tri (o-tolyl) phosphine was added 125 mL of dry tree Ethylamine was added to carry out the reaction. After the crude 4-n-pentylcyclohexyl ester of 4-bromocinnamic acid was completely dissolved, 10.8 g of acrylic acid was injected into the syringe, and the reaction was further continued at 95 ° C for 2 hours. The resulting dark green reaction mixture was poured into 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered. The resulting solid was dissolved in 500 mL of ethyl acetate, washed sequentially with 1N hydrochloric acid and 5 wt% sodium hydrogencarbonate solution, and then dried with magnesium sulfate. The solvent was distilled off to obtain the compound represented by the formula (A-3) 56 g of a preparation of the compound (yellow solid) was obtained. This crude product was recrystallized from ethanol to obtain 30 g (yield: 55%) of a yellow powder of the compound (A-3).

Synthesis Example A-4

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, And then 157.1 g of 4,4-trifluorobutane was added and the reaction was carried out at 100 占 폚 for 5 hours with stirring. After completion of the reaction, the reaction mixture was poured into water to effect reprecipitation. Then, to the obtained precipitate, 48 g of sodium hydroxide and 400 mL of water were added, 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 collected and recrystallized from ethanol to obtain 110 g of white crystals of 4- (4,4,4-trifluorobutoxy) benzoic acid.

12.41 g of this 4- (4,4,4-trifluorobutoxy) benzoic acid was placed in a reaction vessel, to which 100 mL of thionyl chloride and 77 μL of N, N-dimethylformamide were added, followed by stirring at 80 ° C for 1 hour . Then, thionyl chloride was distilled off under reduced pressure, and methylene chloride was added thereto. The organic layer was washed with an aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate, and then the solvent was distilled off. The resulting solid was dissolved in tetrahydrofuran to form a solution.

Next, in a 500 mL three-neck flask different from the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran, and 100 mL of water were placed. While the aqueous solution was ice-cooled, the tetrahydrofuran solution 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 for neutralization, extraction was performed with ethyl acetate, and the organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. The resulting solid was recrystallized from ethanol to obtain 10.0 g of a white crystal of the compound (A-4).

Synthesis Example A-5

31 g of 1-bromo-4- (4-n-pentylcyclohexyl) benzene, 0.23 g of palladium acetate, 1.2 g of tri (o-tolyl) phosphine 1.2 , 56 mL of triethylamine, 8.2 mL of acrylic acid and 200 mL of N, N-dimethylacetamide were placed, and the reaction was carried out at 120 ° C for 3 hours with stirring. After completion of the reaction, the reaction mixture was filtered, and 1 liter of ethyl acetate was added to the filtrate. The obtained organic layer was washed twice with dilute hydrochloric acid and three times with water, dried with magnesium sulfate, and then the solvent was removed under reduced pressure. The resulting solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of a crystal of the compound (A-5).

Synthesis Examples A-6 and A-7

Except that 28 g of 1-bromo-4- (4-n-propylcyclohexyl) benzene was used in place of 1-bromo-4- (4-n-pentylcyclohexyl) (A-6) and 34 g of 1-bromo-4- (4-n-heptylcyclohexyl) benzene were used in place of the compound (A- 6) and 14 g of a crystal of the compound (A-7), respectively.

Synthesis Example A-8

21 g of 4-n-pentyl-4'-carboxy bicyclohexyl, 80 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were placed in a 300 mL branched flask equipped with a reflux condenser and a nitrogen inlet tube, The reaction was carried out with stirring for a time. After completion of the reaction, thionyl chloride was distilled off from the reaction mixture, and then 150 mL of methylene chloride was added thereto. The obtained organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. To the obtained solid was added 400 mL of tetrahydrofuran.

On the other hand, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran were placed in a 1 L three-necked flask equipped with a dropping funnel and a thermometer. Then, the above tetrahydrofuran solution was added dropwise over 3 hours, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or lower. Then, 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. The resulting solid was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 21 g of a compound (A-8).

&Lt; Synthesis of polyorganosiloxane (A) >

Synthesis Example S-1

5.0 g of polyorganosiloxane (EPS-1) having epoxy group obtained in Synthesis Example E-1, 46.4 g of methyl isobutyl ketone, 46.4 g of methyl isobutyl ketone, 0.5 g of the above-mentioned Synthesis Example A-1 1.34 g of the compound (A-1) (equivalent to 25 mol% based on the epoxy group of the EPS-1) and 0.13 g of tetrabutylammonium bromide were placed and stirred at 80 DEG C for 12 hours. After completion of the reaction, the precipitate was precipitated again with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed three times with water, and then the solvent was distilled off to obtain a polyorganosiloxane (A) 2.3 g of a white powder of the compound (S-1) was obtained.

Synthesis Examples S-2 to S-33

The polyorganosiloxane (S-2) shown in Table 1 was obtained in the same manner as in Synthesis Example S-1, except that the type and amount of the used carbonic acid used in Synthesis Example S-1 were changed to those shown in Table 1, respectively ) To (S-33) were synthesized.

In the synthesis examples S-3 to S-7, S-17 and S-21, the carbonic acid (A1) and the other carbonic acid (1) Other carbonic acid (2) was used in combination. In Synthesis Examples S-31 to S-33, two types of carbonic acid were used in combination as the carbonic acid (A1).

The amount of the carbonic acid used in Table 1 is in terms of mol% based on the epoxy group of EPS-1.

The abbreviations of the carbonic acid in Table 1 are as follows.

[Carbonic acid (A1)]

A-1: Compound (A-1) obtained in Synthesis Example A-

A-2: The compound (A-2) obtained in the above Synthesis Example A-

A-3: Compound (A-3) obtained in Synthesis Example A-3,

A-4: Compound (A-4) obtained in Synthesis Example A-4,

A-5: Compound (A-5) obtained in Synthesis Example A-5

A-6: Compound (A-6) obtained in Synthesis Example A-6,

A-7: Compound (A-7) obtained in Synthesis Example A-7,

A-8: Compound (A-8) obtained in Synthesis Example A-8,

[Other carbonic acid (1)]

B-1: Stearic acid

B-2: 1,4-butane diacid mono (3-cholestanyl) ester

B-3: 4- (4,4,4-Trifluorobutoxy) benzoic acid

[Other carbonic acid (2)]

C-1: 3,5-dinitrobenzoic acid

&Lt; Synthesis of polyimide (B) >

Synthesis Examples P-1 to P-29

In these synthesis examples, each polymer as the polyimide (B) was synthesized by the following procedure.

As the monomers, tetracarboxylic acid dianhydrides and diamines of the kinds and amounts shown in Table 2 were used, respectively. The amount of each monomer in Table 2 was expressed in terms of mol% when the amount of tetracarboxylic acid dianhydride was 100 mol%.

The monomer mixture comprising the tetracarboxylic acid dianhydride and the diamine was dissolved in N-methyl-2-pyrrolidone to prepare a solution having a monomer concentration of 20% by weight. The solution was allowed to react at 60 캜 for 4 hours, Was obtained, respectively. The solution viscosity of each polyamic acid solution is shown in Table 2.

Next, N-methyl-2-pyrrolidone was added to each of the obtained polyamic acid solutions to dilute the polyamic acid concentration to 10 wt%, and further pyridine and acetic anhydride were added to the polyamic acid solution 2, and dehydration ring-closure reaction was carried out at 100 ° C for 4 hours. Subsequently, the solvent in the reaction system was replaced with fresh N-methyl-2-pyrrolidone to prepare a solution containing about 20% by weight of the polyimides (PI-1) to (PI-29) &Lt; / RTI &gt; The imidization ratios of the respective polyimides contained in these solutions are shown in Table 2.

&Lt; Synthesis of other polyamic acid >

Synthesis Examples p-1 to p-5

In the same manner as in the synthesis of the polyimide (B) except that tetracarboxylic acid dianhydride and diamine of the kind and amount shown in Table 2 were used in the synthesis of the polyimide (B), polyamic acid (pa-1) to (pa-5), respectively. The solution viscosity of each polyamic acid solution is shown in Table 2.

These polyamic acid solutions were not subjected to dilution with N-methyl-2-pyrrolidone and dehydration ring-closure reaction, but were directly supplied to the preparation of a liquid crystal aligning agent.

&Lt; Synthesis of other polyimide >

Synthesis Examples p-6 to p-8

In the synthesis of the polyimide (B), polyamic acid was obtained in the same manner as in the synthesis of polyimide (B) except that tetracarboxylic acid dianhydride and diamine of the kind and amount shown in Table 2 were used, To obtain a solution containing the solution in weight%. The solution viscosity of each polyamic acid solution is shown in Table 2.

Subsequently, a solution containing 20 wt% of polyimides (pi-1) to (pi-3), which are other polyimides, was obtained in the same manner as in the synthesis of polyimide (B) . The imidization ratios of the respective polyimides contained in these solutions are shown in Table 2.

The abbreviations of the monomers in Table 2 are as follows.

[Tetracarboxylic acid dianhydride]

t1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

t2: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

t3: pyromellitic acid dianhydride

[Diamine]

- diamine (1) -

a: a compound represented by the above formula (b1-1-4)

b: Compound represented by the above formula (b1-1-7)

c: 3,5-Diaminobenzoic acid-3-cholestanyl

d: 2,4-Diamino-3-cholestanyloxybenzene

- diamine (2) -

e: 3,5-diaminobenzoic acid

f: 3,3'-dicarboxy-4,4'-diaminobiphenyl

g: bis (4-aminophenyl) bis (2-carboxyethyl) methane

- diamine (3) -

h: N- (2,4-diaminophenyl) piperidine

i: 4,4'-diaminodiphenylmethane

j: p-phenylenediamine

k: 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-

l: N, N'-bis (4-aminophenyl) piperidine

m: 2,2'-dimethyl-4,4'-diaminobiphenyl

n: 4,4'-diaminodiphenyl ether

&Lt; Preparation and evaluation of liquid crystal aligning agent >

Example 1

[Preparation of liquid crystal aligning agent]

The polyorganosiloxane (S-1) obtained in Synthesis Example S-1 was added to a solution containing the polyimide (PI-1) obtained in Synthesis Example P-1, and the polyorganosiloxane 10 parts by weight based on 100 parts by weight of N-methyl-2-pyrrolidone and butyl cellosolve were further added in a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 40: So as to obtain a solution having a solid concentration of 6.5% by weight. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent for printability evaluation.

A liquid crystal aligning agent for the production of a liquid crystal display element was prepared in the same manner as above except that the solid concentration was adjusted to 3.5 wt%.

[Evaluation of printability]

("Micropearl EX-0041-AC4", manufactured by Sekisui Chemical Co., Ltd.) having a diameter of about 4.1 탆 was dispersed on a silicon wafer of 6 inches and dispersed on a hot plate set at 120 캜 Minute heat treatment was performed to prepare a silicon wafer having a fixing spacer. Using a liquid crystal aligning agent for evaluating printing properties prepared above, the composition was applied onto a silicon wafer with the fixing spacer by a liquid crystal alignment film printing machine (manufactured by Nihon Sha Sein Insights Co., Ltd.) and heated on a hot plate at 80 ° C for 1 minute Baked) to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post baking) to form a coating film having an average thickness of 800 Å. The coating film was observed with a microscope having a magnification of 20 times to evaluate the printability. The evaluation was carried out in accordance with the printing unevenness and the presence or absence of cissing in the fixing spacer portion. When printing unevenness and unevenness of the fixing spacer portions were not observed at all, printing difficulty was observed, The case where it was judged that there was no coating failure was evaluated as the printing property &quot; good &quot;, and the case where a lot of printing unevenness and clinging of the fixing spacer portion were observed was evaluated as &quot; poor &quot;

[Production of liquid crystal display device]

On the transparent electrode surface of the glass substrate with transparent electrode made of ITO film, the liquid crystal aligning agent for liquid crystal display element preparation prepared above was applied by a spinner and pre-baked on a hot plate at 80 DEG C for 1 minute, And then heated in a nitrogen-substituted oven at 200 DEG C for 1 hour to form a coating film having a thickness of 0.08 mu m. Subsequently, a polarizing ultraviolet ray (500 J / m 2) including a bright line of 313 nm was irradiated onto the surface of the coating film from an angle of 40 ° from the substrate normal using an Hg-Xe lamp and a Gantry prism to form a liquid crystal alignment film. The same operation was repeated to obtain 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 periphery of the surface having one liquid crystal alignment film among the pair of substrates by screen printing and then the liquid crystal alignment film faces of the pair of substrates were arranged face to face So that the projection direction of the optical axis of the ultraviolet rays of each substrate to the substrate surface was anti-parallel, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 캜 and slowly cooled to room temperature. Next, the polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other, and the optical axis of the ultraviolet ray of the liquid crystal alignment film was aligned at an angle of 45 degrees with respect to the projection direction to the substrate surface.

This liquid crystal display element was evaluated by the following method. The composition and evaluation results of the liquid crystal aligning agent are shown in Table 3.

[Evaluation of liquid crystal display element]

1) Evaluation of Pretilt Angle

The liquid crystal display device manufactured as described above was subjected to crystal rotation using He-Ne laser light in accordance with the method described in Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys. Vol. 19, p2013 The pretilt angle was measured by the method.

(2) Evaluation of Voltage Conservation Rate

A voltage of 5 V was applied to the liquid crystal display device prepared above at an environmental temperature of 60 캜 for an application time of 60 microseconds and a span of 167 milliseconds and then the voltage maintenance ratio after 167 milliseconds from the application of the release voltage was measured. The measuring apparatus used was a type "VHR-1" manufactured by Toyo Technica Co., Ltd.

(3) Evaluation of burn-in characteristics by luminance difference

Two liquid crystal display elements were prepared in the same manner as described above. An AC voltage of 10 V was applied to one of them (element A), and an AC voltage of 1 V was applied to another element (element B) at 60 DEG C for 20 hours. Thereafter, when the luminance difference between the element A and the element B observed when the applied voltage is switched to the direct-current voltage of 2.5 V is represented by 256 gradations, the case where the luminance difference is 10 or less is referred to as the burn- Quot ;, and when it exceeds 10, the burn-in property is evaluated as &quot; defective &quot;.

Examples 2 to 129 and Comparative Examples 1 to 7

A liquid crystal aligning agent for producing a liquid crystal display element and a liquid crystal aligning agent for evaluating printing properties were prepared and evaluated in the same manner as in Example 1 except that the kind and amount of the polymer used were changed as shown in Table 3 .

The evaluation results are shown in Table 3.

In Examples 31, 32, 41, 42, 84, 85, 86, 91 and 101, two kinds of polyorganosiloxanes (A) were used respectively, and in Comparative Examples 2 and 3, Respectively.

The abbreviations in the column of the solvent composition have the following meanings respectively.

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

In Table 3, it was confirmed that the liquid crystal aligning agent of the present invention in Examples 1 to 129 exhibited excellent printability even on the surface of a substrate having fine irregularities. It has also become clear that these liquid crystal alignment layers formed of the liquid crystal aligning agent of the present invention exhibit good pretilt angularity and high voltage retention as well as excellent burn-in characteristics. In this respect, it will be easily deduced to those skilled in the art that a liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has excellent display quality and excellent long-term reliability.

On the other hand, the liquid crystal aligning agents belonging to the prior art prepared in the comparative examples could not simultaneously satisfy all of the above characteristics.

Claims (7)

(A) a compound represented by the following formula (A1):

(In the formula (A1), R is a fluorine atom or a cyano group, a is an integer of 0 to 4, and &quot; * &quot;
A polyorganosiloxane having a structure represented by the following formula
(B) tetracarboxylic acid dianhydride and
(b2) a diamine containing a diamine having a carboxyl group and
At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a polyamic acid and a polyimide obtained by dehydrocondensing the polyamic acid
Wherein the liquid crystal aligning agent is a liquid crystal aligning agent. The method according to claim 1,
The diamine may further contain
(b1) an alkyl group having 4 to 20 carbon atoms, an alkoxyl group having 4 to 20 carbon atoms, a group having a structure in which two or more 6-membered rings are connected or a group having a steroid structure
And a liquid crystal aligning agent. 3. The method of claim 2,
The polyorganosiloxane (A)
A polyorganosiloxane having an epoxy group and
The carbonic acid having the structure represented by the formula (A1)
Of a liquid crystal alignment agent. The method of claim 3,
Wherein the diamine (b2) is a diamine represented by the following formula (b2-1):

(In the formula (b2-1), y is an integer of 0 to 2;
x is an integer of 0 to 4, provided that when there are plural x, each x may be the same or different from each other;
R ^I is a single bond, a methylene group, an alkylene group or a cyclohexylene group having 2 to 6 carbon atoms, provided that the alkylene group may be interrupted by an ether bond or an ester bond;
X ^I represents a single bond, methylene group, methylene group, fluoroalkyl, alkylene group having 2 to 4 carbon atoms, fluoroalkyl group having 2 to 4 carbon atoms, an oxygen atom, a carbonyl ^{group, * -COO-, * -OCO-, *} - NH-, ^* -CONH-, -NHCO- ^* (in the above, "*", then this indicates that this combination hand attached toward the left of the formula (b2-1)), or the following formula (X ^I -1):

(Formula (X ^I -1) of, R ^II is interrupted by a single bond, a methylene group, an alkylene group or a cyclohexylene group having a carbon number of 2 to 6, with the proviso that the ether bond or an ester bond during said alkylene group May be present;
R ^III is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group -R ^IV COOH (wherein R ^IV is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms or a cyclohexylene group, The group may be interrupted by an ether bond or an ester bond in the middle)
Is a group represented by
The total number of carboxyl groups in the formula (b2-1) is an integer of 1 to 4)
Wherein the liquid crystal aligning agent is a compound represented by the following formula. The method of claim 3,
(B1) the liquid crystal aligning agent, wherein the diamine is a diamine having a group having a steroid structure. A method for forming a liquid crystal alignment film, comprising applying a liquid crystal aligning agent according to claim 1 or 2 to form a coating film, and irradiating the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent according to claim 1 or 2.