KR20160086793A - Liquid crystal aligning agent, process for forming liquid crystal aligning film, liquid crystal display device, and polyorganosiloxane - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent capable of forming a liquid crystal aligning film that shows good liquid crystal aligning ability by a photo-aligning process at a low light dose and has excellent various properties, such as electrical properties. The liquid crystal aligning agent comprises a radiation-sensitive polyorganosiloxane having a specific group represented by the group as depicted by chemical formula. The liquid crystal aligning agent according to the present invention can be preferably applied to liquid crystal display devices having a TN, STN or IPS type liquid crystal cells, and is particularly preferred for a horizontal electric field-type liquid crystal display device having an IPS type liquid crystal cell. In the above chemical formula, * represents a binding arm.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning agent, a liquid crystal aligning agent, a liquid crystal aligning agent, a liquid crystal display element and a polyorganosiloxane,

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

Until now, nematic liquid crystals having a positive dielectric anisotropy were made into a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and TN ( (Twisted Nematic) type and STN (Super Twisted Nematic) type, IPS (In Plane Switching) type which applies an electric field in a direction parallel to the substrate by forming electrodes only on one side of the substrate, and nematic type liquid crystal having negative dielectric anisotropy And VA (Vertical Alignment) type liquid crystal display devices having various liquid crystal cells are known (see Patent Documents 1 to 4). Among the above, a liquid crystal display element having an IPS type liquid crystal cell is known as a liquid crystal display element of a lateral electrolytic method.

In such a liquid crystal cell, a liquid crystal alignment film is provided on the surface of the substrate in order to orient the liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is formed by a method (rubbing method) of rubbing the surface of the organic film formed on the substrate surface with a cloth such as rayon in one direction in a liquid crystal cell of TN type, STN type and IPS type. However, when the formation of the liquid crystal alignment film is performed by rubbing treatment, since dust and static electricity tend to be generated during the rubbing process, dust adheres to the surface of the alignment film, which causes display defects. ) Device, circuit breakage of the TFT element occurs due to the generated static electricity, which is a cause of lowering the product yield. In addition, in a liquid crystal display device which tends to have higher precision in the future, it is difficult to perform uniform rubbing treatment due to irregularities that are inevitably generated on the substrate surface due to high density of pixels.

Therefore, as a separate means for aligning liquid crystals in a liquid crystal cell, there has been proposed a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized light or unpolarized light to a photosensitive organic thin film formed on a substrate surface (see Patent Documents 5 to 8) 15). According to this technique, uniform liquid crystal alignment can be realized without generating static electricity or dust. This technique can be applied to liquid crystal cells of VA type, in addition to liquid crystal cells of TN type, STN type and IPS type.

Recently, it has been reported that a liquid crystal alignment film having good electrical characteristics is obtained by the photo alignment method by using an azo compound specific to the liquid crystal aligning agent used for the TN type liquid crystal cell (Patent Document 16). However, according to this technology, since a high integrated exposure amount of 10,000 J / m < 2 > or more is required for forming a liquid crystal alignment film, the degree of damage of the exposure apparatus over time is large and the manufacturing cost of the liquid crystal alignment film becomes expensive It implies.

It has also been reported that a liquid crystal aligning agent containing a polymer having a specific long-chain structure or a cyclic structure provides a liquid crystal alignment film excellent in liquid crystal alignability and electrical characteristics by an optical alignment method with a small exposure dose (Patent Documents 17 to 19). When applied to a liquid crystal display device having a VA-type liquid crystal cell, this technique is an excellent technology that can easily and inexpensively form a liquid crystal alignment film having a desired performance. However, the liquid crystal alignment film having a TN-, STN- or IPS- When applied to a display device, the liquid crystal alignability is not necessarily sufficient.

It is possible to provide a liquid crystal alignment film excellent in liquid crystal alignability and electrical characteristics by a photo alignment method with a small exposure dose when applied to a liquid crystal display device having a TN type, STN type or IPS type liquid crystal cell, The liquid crystal aligning agent is not yet known.

Japanese Patent Laid-Open No. 56-91277 Japanese Unexamined Patent Application Publication No. 1-120528 U.S. Patent No. 5,928,733 Japanese Patent Application Laid-Open No. 11-258605 Japanese Patent Application Laid-Open No. 6-287453 Japanese Patent Application Laid-Open No. 10-251646 Japanese Patent Laid-Open No. 11-2815 Japanese Patent Application Laid-Open No. 11-152475 Japanese Patent Application Laid-Open No. 2000-144136 Japanese Patent Laid-Open No. 2000-319510 Japanese Patent Application Laid-Open No. 2000-281724 Japanese Patent Application Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 2003-307736 Japanese Patent Application Laid-Open No. 2004-163646 Japanese Patent Application Laid-Open No. 2002-250924 Japanese Patent Application Laid-Open No. 2007-138138 International Publication No. 2009/025385 International Publication No. 2009/025386 International Publication No. 2009/025388 Japanese Patent Application Laid-Open No. 63-291922

Chemical Reviews, 95, p. 1409 (1995)

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a liquid crystal display device having a TN type, STN type or IPS type liquid crystal cell, which exhibits good liquid crystal alignability by a photo- And a liquid crystal aligning agent capable of forming a liquid crystal alignment film excellent in various performances such as electrical characteristics.

It is another object of the present invention to provide a liquid crystal alignment film and a liquid crystal display element having excellent properties as described above.

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

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

Is obtained by a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane having at least one group selected from the group consisting of the groups represented by the following formulas A1 'and A2', respectively.

[Formula A1 ']

[Formula A2 ']

(Wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, R ¹ is a phenylene group or a cyclohexylene group, provided that the hydrogen atom of the phenylene group or the cyclohexylene group R ² is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-, and a part or all of R ¹ and R ² may be substituted with a fluorine atom or a cyano group, a is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4 , "*" Indicates a binding hand;

In formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R ⁴ is a phenylene group or a cyclohexylene group, provided that the hydrogen atom all or part of may be substituted with a fluorine atom or a cyano group, R ⁵ is a single bond, methylene group, and having 2 or 3 alkylene group, an oxygen atom, a sulfur atom or -NH- in, c is 1 to 3 A plurality of R ⁴ and R ⁵ may be the same or different, R ⁶ is a fluorine atom or a cyano group, d is an integer of 0 to 4, R ⁷ is an oxygen An atom, -COO- + or -OCO - + (provided that the bonding hand having "+" is bonded to R ⁸ ), R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ⁹ represents a single _{bond, + -OCO- (CH 2) f} - or _{+ -O- (CH 2) g -} ( texture pasted on the "+" at the end, over Hand _{^{- (R 7 -R 8) e}} - side and, f and g is an integer of 1 to 10), and, e is an integer from 0 to 3, "*" denotes that the binding sonin)

The above objects and advantages of the present invention are achieved by a liquid crystal alignment layer formed of the above-mentioned liquid crystal aligning agent,

Thirdly, this is achieved by a liquid crystal display element having the liquid crystal alignment film.

When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a TN type, an STN type or an IPS type, particularly a liquid crystal display element of a transverse electrolytic type having a liquid crystal cell of an IPS type, It is possible to form a liquid crystal alignment film exhibiting excellent liquid crystal alignment performance and excellent in various performances such as electrical characteristics.

The liquid crystal display element of the present invention including the liquid crystal alignment layer formed of the liquid crystal aligning agent of the present invention can be applied to various display apparatuses because it can display high quality and is inexpensive.

The liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane having at least one group selected from the group consisting of the groups represented by the above-mentioned formulas A1 'and A2', respectively.

<Radiation-sensitive polyorganosiloxane>

The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is one having at least one group selected from the group consisting of the groups represented by the above formulas A1 'and A2'.

The alkyl group having 1 to 3 carbon atoms represented by R in the formula (A1 ') and R' in the formula (A2 ') is preferably a methyl group, an ethyl group or an n-propyl group. The phenylene group and the cyclohexylene group of R ¹ in the formula (A1 ') and R ⁴ in the formula (A2') are preferably 1,4-phenylene group or 1,4-cyclohexylene group, respectively.

The R ² in the above formula (A1 ') is preferably a single bond, an oxygen atom or -CH = CH-.

Examples of the bivalent aromatic group represented by R ⁸ in the formula (A2 ') include a 1,4-phenylene group and a 4,4'-biphenylene group;

Examples of the divalent alicyclic group include, for example, 1,4-cyclohexylene group, 4,4'-bicyclohexylene group and the like;

Examples of the divalent heterocyclic group include furan-2,5-diyl group, thiophene-2,5-diyl group, 2,2'-bithiophene-5,5'-diyl group and the like;

Examples of the divalent condensed ring group include anthraquinone-2,6-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene- , 7-diyl group, anthracene-9,10-diyl group, carbazole-3,6-diyl group, dibenzothiophene-2,8-diyl group and the like. It is preferable that e in the formula (A2 ') is 0.

Specific examples of the group of the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention include groups represented by the following formulas, for example, as the group represented by the above formula (A1 ');

(Where, "*" indicates a combined hand)

As the group represented by the above formula (A2 '), for example, there can be mentioned a group represented by each of the following formulas.

(Where, "*" indicates a combined hand)

The content ratio of at least one group selected from the group consisting of the groups represented by the above formulas A1 'and A2' in the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably 0.2 to 6 mmol / g -Polymer, more preferably 0.3 to 5 mmol / g-polymer.

The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention preferably has an epoxy group in addition to at least one group selected from the group consisting of the groups represented by the above-mentioned formulas A1 'and A2'. In this case, the epoxy equivalent of the radiation-sensitive polyorganosiloxane is preferably 150 g / mol or more, more preferably 200 to 10,000 g / mol, and still more preferably 200 to 2,000 g / mol. By using an epoxy equivalent of a radiation-sensitive polyorganosiloxane in such a ratio, the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film having excellent liquid crystal alignability and excellent afterimage characteristics without impairing the storage stability of the liquid crystal aligning agent So that it is preferable.

The weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography of the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000 , Particularly preferably from 3,000 to 30,000.

<Synthesis of radiation-sensitive polyorganosiloxane>

The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention may be one synthesized by any method as long as it is as described above. As a method of synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, for example,

A method of hydrolyzing and condensing a hydrolyzable silane compound having at least one group selected from the group consisting of the groups represented by the above formulas A1 'and A2', a mixture of the hydrolyzable silane compound and another hydrolyzable silane compound,

A method of reacting at least one member selected from the group consisting of a polyorganosiloxane having an epoxy group and a compound represented by each of the following formulas (A1) and (A2), or the like.

(A1)

(A2)

(R, R ¹ , R ² , R ³ , a and b in formula (A1) have the same meanings as those in formula (A1 '), respectively;

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , c, d and e in formula (A2) are the same as those in formula (A2 '

Of these, the latter method is preferred from the viewpoints of ease of synthesis of the starting compound, ease of reaction, and the like.

Hereinafter, the polyorganosiloxane having an epoxy group, which is a preferred method for synthesizing the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, and the compound selected from the group consisting of the compounds represented by the above formulas A1 and A2 At least one kind of reaction method will be described.

[Polyorganosiloxane Having an Epoxy Group]

The epoxy group in the epoxy group-containing polyorganosiloxane is preferably a group in which an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton is directly bonded to a silicon atom through an alkylene which may be interrupted by an oxygen atom A group having an epoxy group) and is preferably present in the polyorganosiloxane. Examples of the group having such an epoxy group include groups represented by the following formulas (EP-1) and (EP-2).

(In the formulas (EP-1) and (EP-2), "*"

The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol.

The weight average molecular weight of the polyorganosiloxane having an epoxy group in terms of polystyrene measured by gel permeation chromatography is preferably 500 to 100,000, more preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000 .

The polyorganosiloxane having such an epoxy group can be produced, for example, by reacting a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group with another silane compound, preferably in the presence of an appropriate organic solvent, water and a catalyst, .

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

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (triple 2- (trifluoromethyl) ethyl triethoxysilane, 2- (trifluoromethyl) ethyl tri-n-propoxysilane, 2- (trifluoromethyl) ethyl tri (trifluoromethyl) ethyl tri-n-butoxysilane, 2- (trifluoromethyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- N-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro- (Perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri- Octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyl tri-sec-butoxysilane, 2- (perfluoro- Methoxy silane, 2- (perfluoro-n-octyl) ethyl triethoxy silane,

Octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro- ) Ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, Hydroxymethyltri-sec-butoxysilane, hydroxymethyltri-sec-butoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-sec-butoxysilane, 3- ( (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropyltri-sec-butoxysilane, 3 (meth) acryloxypropyltri-i-propoxysilane, 3- - mercaptopropyl tri Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3 Mercaptopropyltrimethoxysilane, mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltris-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, allyltrichlorosilane, allyl N-butoxysilane, allyltri-sec-butoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri- Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxy But are not limited to, phenyl tri-sec-butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi- Silane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, Silane, dimethyl di-sec-butoxysilane,

(Perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, N-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] N-octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro- (Methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, Propoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, Diethoxysilane, (methyl) (vinyl) di-n- (Methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, (vinyl) di- Divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec- Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, di Ethoxytrimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propyltrimethylsilane, n-propyltrimethylsilane, Propoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (Methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) In addition to the silane compound having one silicon atom such as diphenylsilane,

X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, K- X-22-170BX, X-22-170D, X-22-170DX, X-22-170B, X-21-5846, X- X-22-176D, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X- KR-200, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR- KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shinetsu Chemical Industry Co., Ltd.); Glass resin (manufactured by Showa Denko K.K.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (manufactured by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (manufactured by Nippon Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931 and XMS-5025 (manufactured by Chisso Corporation); Methyl silicate MS51, methyl silicate MS56 (manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (trade name, manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko K.K.), and the like, and at least one of them may be used.

Examples of other silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylate Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, At least one member selected from the group consisting of a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, .

When synthesizing a polyorganosiloxane having an epoxy group in the present invention, it is preferable to prepare and set such that the epoxy equivalent of the polyorganosiloxane in which the ratio of the silane compound having an epoxy group and the other silane compound is obtained falls within the above- Do.

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

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

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

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

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

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

The amount of the organic solvent used is preferably 10 to 10,000 parts by weight based on 100 parts by weight of the total of the silane compounds (total amount of the silane compound having an epoxy group and other silane compounds optionally used) Is from 50 to 1,000 parts by weight.

The amount of water used when synthesizing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the total amount of the silane compound.

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

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

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

As a catalyst for synthesizing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, a desired polyorganosiloxane can be obtained at a rapid hydrolysis and condensation rate without causing a side reaction such as ring opening of an epoxy group, . The liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a derivative of a cinnamic acid derivative is preferable because of excellent storage stability. This is because, as indicated in Non-Patent Document 1 (Chemical Reviews, 95, p. 1409 (1995)), when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis and condensation reaction, , A ladder-type structure or a basket-like structure is formed, and a polyorganosiloxane having a small content of silanol groups is obtained. The condensation reaction between the silanol groups is suppressed because the content of the silanol groups is small and when the liquid crystal aligning agent of the present invention contains the other polymer described later, the condensation reaction between the silanol groups and the other polymer is inhibited, It is presumed that this is an excellent result.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature and the like, and should be appropriately set. For example, the amount is preferably 0.01 to 3 moles per 1 mole of the total amount of the silane compound, 0.05 to 1 mol.

The hydrolysis and condensation reaction in the synthesis of a polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, mixing this solution with an organic base and water, For example, by heating using a suitable heating device such as an oil bath.

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 not be stirred or stirred, or the mixed solution may be placed under reflux.

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

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

[Compound represented by each of formulas (A1) and (A2)

Specific examples of the compound represented by each of the above formulas A1 and A2 include a carboxylic acid formed by bonding a hydrogen atom to the bond of the above-mentioned group as a group represented by each of the above formulas A1 'and A2'.

[Synthesis of radiation-sensitive polyorganosiloxane]

The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of the present invention is preferably selected from the group consisting of a polyorganosiloxane having an epoxy group as described above and a compound represented by each of the above formulas A1 and A2 Can be easily obtained by reacting at least one of them in the presence of a catalyst and an organic solvent.

Here, at least one member selected from the group consisting of the compounds represented by the above formulas (A1) and (A2) is preferably used in an amount of 0.001 to 10 moles, more preferably 0.01 to 10 moles per mole of the epoxy group of the polyorganosiloxane To 5 moles, more preferably 0.05 to 2 moles, particularly preferably 0.05 to 0.8 moles.

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

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

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

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

Quaternary organic amines such as tetramethylammonium hydroxide are preferred.

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

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

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphor 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;

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

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

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

Boron compounds such as boron trifluoride, triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

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

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

Amine salt type latent curing accelerator;

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

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

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

The reaction of at least one selected from the group consisting of the polyorganosiloxane having an epoxy group and the compound represented by each of the above formulas A1 and A2 may be carried out in the presence of an organic solvent if necessary. Examples of such an organic solvent include hydrocarbons, ethers, esters, ketones, amides, and alcohols. Of these, ethers, esters or ketones are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent is used in such a ratio that the solid concentration (the ratio of the weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight.

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

The above-described radiation-sensitive polyorganosiloxane can be synthesized by a ring-opening addition reaction of an epoxy having a polyorganosiloxane having an epoxy group to at least one kind selected from the group consisting of the groups represented by the above-mentioned formulas A1 'and A2' Is introduced. This synthesis method is a very preferable method because it is simple and can increase the introduction ratio of at least one group selected from the group consisting of the groups represented by each of the formulas A1 'and A2'.

<Other ingredients>

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

The liquid crystal aligning agent of the present invention may contain, in addition to the above-mentioned radiation-sensitive polyorganosiloxane, another component as long as the effect of the present invention is not impaired. Examples of such other components include a polymer other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as "another polymer"), a curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (Excluding those corresponding to the radiation-sensitive polyorganosiloxane, hereinafter referred to as "epoxy compound"), a functional silane compound (excluding those corresponding to the radiation-sensitive polyorganosiloxane), a surfactant, and the like .

[Other Polymers]

The other polymer can be used to further improve the solution characteristics of the liquid crystal aligning agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. Examples of the other polymer include at least one polymer selected from the group consisting of polyamic acid and polyimide, a polyorganosiloxane other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polyorganosiloxane" ), Polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates.

{Polyamic acid}

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

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and the like. . Specific examples thereof include aliphatic tetracarboxylic acid dianhydride 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, (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'- dione), 5- (2,5-dioxotetrahydro 3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: - dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6- dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraone, and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like can be mentioned respectively,

Tetracarboxylic acid dianhydrides described in Patent Documents 17 to 19 can be used.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid preferably includes an alicyclic tetracarboxylic acid dianhydride, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1, 2,3,4-cyclobutanetetracarboxylic acid dianhydride, and more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. Do.

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride Is contained in an amount of preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 2,3,5-tricarboxycyclopentylacetic acid dianhydride And most preferably at least one selected from the group consisting of water and 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride.

Examples of diamines used for synthesizing polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine 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-phenyl (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-diaminocyclohexane, N, N'- Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Stearyloxy-3,5-diaminobenzene, cholestanyloxy-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 , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 1, 1-bis (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1 , 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- Cyclohexane) cyclohexane and a compound represented by the following formula (D-1);

Of (formula (D-1), X ^I is an alkyl group having 1 to 3, * -O-, * -COO- or * -OCO- (so long as those hands coupling attached the "*" in combination with a diamino group ), H is 0 or 1, i is an integer of 0 to 2, and j is an integer of 1 to 20)

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

The diamines described in Patent Documents 17 to 19 can be used.

X ^I in the above formula (D-1) is preferably in the carbon number of alkyl group of from 1 to 3, * -O- or * -COO- (hereinafter coupling end, and coupling the hand-diamino phenyl group attached to "*") . Specific examples of the group C _j H _{2j + 1} - include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-pentyl group, N-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-hexadecyl group, n-hexadecyl group, an n-nonadecyl group, and an n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the above formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4), and the like.

In the above formula (D-1), it is preferable that h and i are not 0 at the same time.

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

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

The synthesis reaction of the polyamic acid is carried out preferably in an organic solvent at a temperature of preferably -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably 2 to 10 hours Lt; / RTI &gt; The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, , Non-protonic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide,? -Butyrolactone, tetramethyl urea, and hexamethylphosphotriamide;

phenol-based solvents such as m-cresol, xylenol, phenol, halogenated phenol and the like. The amount (a) of the organic solvent to be used is preferably 0.1 to 50% by weight, more preferably 5 to 20% by weight, based on the total amount (a + b) of the reaction solution and the total amount of the tetracarboxylic acid dianhydride and the diamine compound 30% by weight.

In this way, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be used as it is for preparing a liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and used for the preparation of a liquid crystal aligning agent, or after the isolated polyamic acid is purified, .

When the polyamic acid is subjected to dehydration cyclization to form a polyimide, the reaction solution may be used as it is for the dehydration ring closure reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then used for dehydration ring closure reaction, May be used for the dehydration ring-closing reaction after purification.

The isolation of the polyamic acid can be carried out by pouring the reaction solution into a large amount of a poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or a method of distilling off the organic solvent in the reaction solution under reduced pressure using an evaporator. The polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent, followed by precipitation with a poor solvent, or a step of distillation under reduced pressure using an evaporator once or several times.

{Polyimide}

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

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

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

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

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

{Other polyorganosiloxane}

Another polyorganosiloxane in the present invention is a polyorganosiloxane other than the above-mentioned radiation-sensitive polyorganosiloxane. Such another polyorganosiloxane is preferably prepared by dissolving at least one silane compound (hereinafter also referred to as "raw silane compound") selected from the group consisting of an alkoxysilane compound and a halogenated silane compound in an appropriate organic solvent, And hydrolysis and condensation in the presence of a catalyst.

Examples of the raw material silane compound used herein include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- Ethoxy silane, tetra-tert-butoxy silane, tetrachlorosilane; Butoxysilane, methyltri-sec-butoxysilane, methyltri-sec-butoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri- propyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopropoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-tert-butoxy silane, ethyl trichlorosilane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl trichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and the like, and it is preferable to use at least one of them. In particular, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, It is preferable to use at least one member selected from the group consisting of ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane .

Other polyorganosiloxanes in the present invention can be synthesized in the same manner as described above as a method for synthesizing a polyorganosiloxane having an epoxy group, except that the raw silane compound as described above is used.

The weight average molecular weight of the other polyorganosiloxane in terms of polystyrene measured by gel permeation chromatography is preferably 1,000 to 100,000, more preferably 5,000 to 50,000.

{Use ratio of other polymer}

In the case where the liquid crystal aligning agent of the present invention contains other polymers together with the above-mentioned radiation-sensitive polyorganosiloxane, the proportion of the other polymer used is not more than 10,000 parts by weight based on 100 parts by weight of the radiation-sensitive polyorganosiloxane desirable. A more preferable use ratio of the other polymer differs depending on the kind of the other polymer.

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

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

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

[Curing agent and curing catalyst]

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

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

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

Specific examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid- 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride and the like, and examples of other polycarboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methyl Tetracarboxylic acid dianhydride generally used in the synthesis of a compound represented by the following formula (CA-1), and polyamic acid, which is a compound represented by the following formula (CA-1), dodecenylsuccinic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride Aldehyde reaction products of alicyclic compounds having a conjugated double bond such as? -Terpinene and alo cymene and maleic anhydride, and hydrogenated products thereof, in addition to water.

(In the formula (CA-1), k is an integer of 1 to 20)

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

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

A quaternary compound;

Quaternary amine compounds;

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

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

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

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

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

Amine salt type latent curing accelerator;

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

[Epoxy Compound]

The epoxy compound can be contained in the liquid crystal aligning agent of the present invention from the viewpoint of improving the 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-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- -Aminomethylcyclohexane and the like can be preferably used.

When the liquid crystal aligning agent of the present invention contains an epoxy compound, the content thereof is preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the above-mentioned radiation-sensitive polyorganosiloxane and optionally other polymer, More preferably 0.1 to 30 parts by weight.

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 adhesiveness of the obtained liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- Diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. A reaction product of a tetracarboxylic acid dianhydride and a silane compound having an amino group as described in Patent Document 20 (Japanese Unexamined Patent Publication (Kokai) No. 63-291922) can be used.

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

[Surfactants]

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

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

<Liquid Crystal Aligner>

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

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

The organic solvent preferably usable in the liquid crystal aligning agent of the present invention differs depending on the kind of the other polymer to which it is optionally added.

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

On the other hand, when the liquid crystal aligning agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or a group containing a radiation-sensitive polyorganosiloxane and other polyorganosiloxane but also a polyamic acid and a polyimide Ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, Propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Butyl ether (butyl cell Methylcellosolve acetate, ethylcellosolve acetate, propylcellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol acetate, ethyl cellosolve acetate, ethyl cellosolve acetate, ethyl cellosolve acetate, Butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate , Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, and acetic acid isoammethyl acetate. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-

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

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

The temperature at which the liquid crystal aligning agent of the present invention is produced is preferably 0 to 200 캜, more preferably 0 to 40 캜.

&Lt; Method of forming liquid crystal alignment film &

The liquid crystal aligning agent of the present invention can be obtained by a liquid crystal aligning film, a liquid crystal aligning film having a liquid crystal cell having a TN type or STN type liquid crystal cell, or a liquid crystal alignment film used in a transverse electrolytic liquid crystal display device having an IPS type liquid crystal cell Can be preferably used. The liquid crystal aligning agent of the present invention is particularly preferable when applied to a liquid crystal display device having an IPS type liquid crystal cell because the effect of the present invention can be exerted to the maximum.

In order to form the liquid crystal alignment film by using the liquid crystal aligning agent of the present invention, it can be performed by a method in which the liquid crystal aligning agent of the present invention is coated on the substrate to form a coating film, and the coating film is irradiated with radiation.

Here, when the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a TN type or STN type liquid crystal cell, two substrates on which a patterned transparent conductive film is provided are formed into a pair, The liquid crystal aligning agent of the present invention is applied on the surface to form a coating film. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of IPS type, it is preferable that a substrate having a transparent conductive film or a metal film patterned in a comb- And the liquid crystal aligning agent of the present invention is applied to one surface of the comb-like electrode and one surface of the counter substrate to form a coating film.

In any case, as the above substrate, for example, a transparent substrate including plastics such as glass such as float glass and soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and polycarbonate can be used have. As the transparent conductive film, for example, an ITO film containing In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film containing SnO ₂ , or the like can be used. As the metal film, for example, a film containing a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film includes, for example, a method of forming a transparent conductive film without a pattern and then forming a pattern by a photo-etching method or a sputtering method, a method of using a mask having a desired pattern for forming a transparent conductive film Or the like.

A functional silane compound, titanate, or the like may be previously coated on the substrate and the electrode in order to improve the adhesiveness between the substrate or the conductive film or the electrode and the coated film when the liquid crystal aligning agent is applied onto the substrate.

The application of the liquid crystal aligning agent onto the substrate can be preferably carried out by an appropriate application method such as offset printing, spin coating, roll coatering, or inkjet printing, followed by preheating (prebaking) the coated surface, Followed by baking (post-baking) to form a coating film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 캜, and the post-baking condition is preferably 120 to 300 캜, more preferably 150 to 250 캜, preferably 5 to 200 minutes, Is 10 to 100 minutes. The thickness of the coating film after the post-baking is preferably 0.001 to 1 占 퐉, more preferably 0.005 to 0.5 占 퐉.

The coating film thus formed is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, thereby imparting liquid crystal aligning ability. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from 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.

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

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

<Manufacturing Method of Liquid Crystal Display Element>

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

First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which liquid crystal is sandwiched between the pair of substrates is manufactured. In order to produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method. First, two substrates are opposed to each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together using a sealing agent, and a cell After the liquid crystal is injected and filled in the interval, the injection hole is sealed to manufacture the liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. An ultraviolet light 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 surface and then the other substrate is bonded so that the liquid crystal alignment film is opposed And then irradiating ultraviolet light to the entire surface of the substrate to cure the sealing agent, thereby manufacturing a liquid crystal cell.

In any method, it is preferable that the liquid crystal cell is subsequently heated to a temperature at which the liquid crystal used is isotropic, and then slowly cooled to room temperature to remove the flow orientation upon liquid crystal filling.

Further, by bonding a polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display element of the present invention can be obtained. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate on the two substrates on which the liquid crystal alignment film is formed.

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

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal and the like can be used. It is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal. Examples thereof include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, , Dioxane-based liquid crystals, bicyclooctane-based liquid crystals, quaternary-based liquid crystals, and the like. Further, it is also possible to add a cholesteric liquid crystal such as cholestyl chloride, cholesteryl nonanoate or cholesteryl carbonate to the liquid crystal;

Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck);

and a ferroelectric liquid crystal such as p-disiloxybenzylidene-p-amino-2-methylbutyl cinnamate may be further added.

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

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

[Example]

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

The weight average molecular weights in the following Synthesis Examples are the polystyrene reduced values measured by gel permeation chromatography under the following conditions, respectively.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68 kgf / ㎠

Further, in the following synthesis examples, the synthesis of the raw material compound and the polymer was repeated as necessary with the following synthesis scale to ensure the required amount in the following examples.

<Synthesis Example of Polyorganosiloxane Having an Epoxy Group>

Synthesis Example ES1

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, , And mixed at room temperature.

Subsequently, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was carried out at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral. Then, the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group (ES- 1) was obtained as a viscous transparent liquid.

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

The viscosity, Mw, and epoxy equivalent of the polyorganosiloxane (ES-1) having the epoxy group are shown in Table 1.

Synthesis Examples ES2 to ES3

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

The Mw and the epoxy equivalent of the polyorganosiloxane having these epoxy groups are shown in Table 1.

In Table 1, the abbreviations of the raw material silane compounds are as follows.

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

MTMS: methyltrimethoxysilane

PTMS: phenyltrimethoxysilane

<Synthesis Example of Compound Represented by Formula A1>

(A1-1) to (A1-4) (hereinafter referred to as "compound (A1-1)", "compound (A1- 2) "," compound (A1-3) "and" compound (A1-4) ").

Synthesis Example A1-1

20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were fed into a 500 mL three-necked flask equipped with a cooling tube Mixed, and made into a solution. Subsequently, 7 g of acrylic acid was added to the above solution using a syringe and stirred, followed by reaction at 120 ° C for 3 hours with stirring. After completion of the reaction was confirmed by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. The insoluble matter was filtered off, and the filtrate was poured into 300 mL of 1 N hydrochloric acid, and the precipitate was recovered. This precipitate was recrystallized from a mixed solvent (ethyl acetate: hexane = 1: 1 (volume ratio)) containing ethyl acetate and hexane to obtain 8.4 g of a compound (A1-1).

Synthesis Example A1-2

In a 300 mL three-necked flask equipped with a cooling tube, 6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromominic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, And the mixture was stirred at 80 ° C for 8 hours. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature. The cooled reaction mixture was poured into 200 mL of 1 N hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, washed with 100 mL of 1 N hydrochloric acid, 100 mL of pure water and 100 mL of saturated brine, and then the solvent was distilled off. The resulting solid was vacuum-dried to obtain 9 g of a compound (A1-2).

Synthesis Example A1-3

To a 200 mL three-necked flask equipped with a condenser tube were added 3.6 g of 4-fluorostyrene, 6 g of 4-bromominic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine, 50 mL of acetamide was added and mixed to prepare a solution. This solution was stirred at 120 ° C for 3 hours to carry out the reaction. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and the insoluble material was filtered off. The filtrate was poured into 300 mL of 1 N hydrochloric acid, and the precipitate was recovered. This precipitate was recrystallized from ethyl acetate to obtain 4.1 g of a compound (A1-3).

Synthesis Example A1-4

To a 200 mL three-necked flask equipped with a condenser tube were added 9.5 g of 4-vinylbiphenyl, 10 g of 4-bromominic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, 80 mL of acetamide was added and mixed to obtain a solution. This solution was stirred at 120 ° C for 3 hours to carry out the reaction. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and the insoluble material was filtered off. The filtrate was poured into 500 mL of 1 N hydrochloric acid, and the precipitate was recovered. This precipitate was recrystallized from a mixed solvent (dimethylacetamide: ethanol = 1: 1 (volume ratio)) containing dimethylacetamide and ethanol to obtain 11 g of a compound (A1-4).

&Lt; Synthesis Example of the Compound Represented by the Formula (A2)

(A2-1) and (A2-2), respectively, in the same manner as the following Synthesis Examples A2-1 and A2-2. 2) ") were synthesized.

Synthesis Example A2-1

In a 200 mL three-necked flask equipped with a cooling tube, 10 g of phenyl acrylate, 11.3 g of 4-bromobenzoic acid, 0.13 g of palladium acetate, 0.68 g of tris (2-tolyl) phosphine, 23 g of triethylamine, 100 mL were added and mixed to prepare a solution. This solution was reacted at 120 DEG C for 3 hours with stirring. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature, and the insoluble material was filtered off. The filtrate was poured into 500 mL of 1 N hydrochloric acid, and the precipitate was recovered. This precipitate was recrystallized from ethyl acetate to obtain 9.3 g of compound (A2-1).

Synthesis Example A2-2

10 g of 4-cyclohexylphenol, 6.3 g of triethylamine and 80 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask equipped with a dropping funnel and mixed. This was cooled with an ice bath, and a solution containing 5.7 g of acryloyl chloride and 40 mL of dehydrated tetrahydrofuran was added dropwise from a dropping funnel. After completion of dropwise addition, the mixture was stirred in an ice bath for 1 hour, then returned to room temperature, and the reaction was carried out with stirring for further 2 hours. After completion of the reaction, the reaction mixture was filtered and the resulting salt was removed. Ethyl acetate was added to the filtrate, and the organic layer was washed with water. The solvent was removed under reduced pressure and the residue was dried to obtain 12.3 g of 4-cyclohexylphenyl acrylate as an intermediate.

Subsequently, in a 100 mL three-necked flask equipped with a cooling tube, 6 g of 4-cyclohexylphenyl acrylate, 5.7 g of 2-fluoro-4-bromobenzoic acid, 0.06 g of palladium acetate, 0.32 g of phosphine, 11 g of triethylamine and 50 mL of dimethylacetamide were charged and mixed to prepare a solution. This solution was reacted at 120 DEG C for 3 hours with stirring. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature, and the insoluble material was filtered off. The filtrate was poured into 300 mL of 1 N hydrochloric acid, and the resulting precipitate was recovered. This precipitate was recrystallized from ethyl acetate to obtain 3.4 g of a compound (A2-2).

<Comparative Synthesis Example of Carboxylic Acid>

Synthesis Example RA1

11.21 g of 4-hydroxycalcone, 8.35 g of ethyl bromoacetate, 13.8 g of potassium carbonate and 100 mL of dimethylacetamide were added to a 200-mL three-necked flask, and the mixture was reacted at 120 DEG C for 7 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature, to which 100 mL of ethyl acetate was added, and the obtained organic layer was washed with water. After the solvent was removed from the obtained organic layer under reduced pressure, the organic layer was dried and recrystallized from a mixed solvent (ethanol: water = 4: 1 (volume ratio)) containing ethanol and water to obtain 11.4 g of intermediate chalconyloxyacetate .

In a 500 mL three-necked flask equipped with a cooling tube, 6.2 g of sodium chalconyl oxyacetate, 2 g of sodium hydroxide, 200 mL of ethanol and 50 mL of water were added and mixed, and the mixture was reacted under reflux for 3 hours . After completion of the reaction, the reaction mixture was cooled, acidified with dilute hydrochloric acid, and extracted with 500 mL of ethyl acetate. The obtained organic layer was washed with water and then the solvent was removed under reduced pressure to dryness to obtain 4.1 g of a compound represented by the following formula (RA-1) (compound (RA-1)).

&Lt; Synthesis Example of a Radiation-Sensitive Polyorganosiloxane >

Synthesis Example S1

9.3 g of the polyorganosiloxane (ES-1) having an epoxy group obtained in Synthesis Example ES1, 26 g of methyl isobutyl ketone, 3 g of the compound (A1-1) obtained in Synthesis Example A1-1 And 0.10 g of UCAT 18X (trade name, a quaternary amine salt manufactured by SANA PRO), and the reaction was carried out at 80 ° C for 12 hours with stirring. After the completion of the reaction, the reaction mixture was poured into methanol to recover the resulting precipitate. The resulting precipitate was dissolved in ethyl acetate to prepare a solution. The solution was rinsed three times, and the solvent was distilled off to obtain a radiation-sensitive polyorganosiloxane ( S-1) as a white powder. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-1) was 3,500.

Synthesis Example S2

The same procedure as in Synthesis Example S1 was carried out except that 3 g of the compound (A1-2) obtained in Synthesis Example A1-2 was used instead of the compound (A1-1) in Synthesis Example S1 to obtain a radiation-sensitive polyorganosiloxane (S -2) as white powder. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-2) was 4,900.

Synthesis Example S3

The same procedure as in Synthesis Example S1 was carried out except that 4 g of the compound (A1-3) obtained in Synthesis Example A1-3 was used instead of the compound (A1-1) in Synthesis Example S1 to obtain a radiation-sensitive polyorganosiloxane (S -3) of white powder. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-3) was 5,000.

Synthesis Example S4

The same procedure as in Synthesis Example S1 was carried out except that 4 g of the compound (A1-4) obtained in Synthesis Example A1-4 was used instead of the compound (A1-1) in Synthesis Example S1 to obtain a radiation-sensitive polyorganosiloxane (S -4) as white powder. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-4) was 4,200.

Synthesis Example S5

10.5 g of the polyorganosiloxane (ES-2) having an epoxy group obtained in the above Synthesis Example ES2 was used instead of the polyorganosiloxane (ES-1) having an epoxy group in Synthesis Example S1, 7.0 g of a white powder of a radiation-sensitive polyorganosiloxane (S-5) was obtained in the same manner as in Synthesis Example S1 except that 3.35 g of the compound (A2-1) obtained in Example A2-1 was used. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-5) was 5,500.

Synthesis Example S6

11.4 g of the polyorganosiloxane (ES-3) having an epoxy group obtained in the above Synthesis Example ES3 was used instead of the polyorganosiloxane (ES-1) having an epoxy group in Synthesis Example S1, 9.6 g of a white powder of a radiation-sensitive polyorganosiloxane (S-6) was obtained in the same manner as in Synthesis Example S1 except that 4.6 g of the compound (A2-2) obtained in Example A2-3 was used, respectively. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (S-6) was 7,400.

&Lt; Comparative synthesis example of radiation-sensitive polyorganosiloxane >

Synthesis Example RS1

Except for using 4.4 g of a compound represented by the following formula synthesized according to the method described in Patent Document 17 (International Publication No. 2009/025385) instead of the compound (A1-1) in Synthesis Example S-1, In the same manner as in S1, 7.2 g of a white powder of a radiation-sensitive polyorganosiloxane (RS-1) was obtained. The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (RS-1) was 9,400.

Synthesis Example RS2

(RS-2) was obtained in the same manner as in Synthesis Example S1, except that 3.52 g of the compound (RA-1) obtained in Synthesis Example RA1 was used instead of the compound (A1-1) ) Of a white powder (9.1 g). The weight average molecular weight Mw of this radiation-sensitive polyorganosiloxane (RS-2) was 6,900.

&Lt; Synthesis Example of Other Polymers >

[Synthesis example of polyamic acid]

Synthesis Example pa1

19.61 g (0.1 mole) of cyclobutane tetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'-dimethylbiphenyl were added to 367.6 g of N-methyl- And the reaction was carried out at room temperature for 6 hours. The reaction mixture was poured into a very large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid (pa-1).

Synthesis Example pa2

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 14.23 g (0.1 mole) of cyclohexane bis (methylamine) were dissolved in 329.3 g of N-methyl-2-pyrrolidone, Lt; 0 &gt; C for 6 hours. The reaction mixture was poured into a very large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 32 g of polyamic acid (pa-2).

[Example of synthesis of polyimide]

Synthesis Example pi-1

17.5 g of the polyamic acid pa-2 obtained in Synthesis Example pa-2 was dissolved in 232.5 g of N-methyl-2-pyrrolidone, and 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto. Deg.] C for a period of time. After completion of the reaction, the reaction mixture was poured into excess methanol and the reaction product was precipitated. The precipitate was collected, washed with methanol, and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (pi-1).

[Synthesis example of other polyorganosiloxane]

Synthesis Example s1

11 g of white powder of another polyorganosiloxane (s-1) was obtained in the same manner as in Synthesis Example S1, except that 5 g of lauric acid was used in place of the compound (A1-1) in Synthesis Example S1. The weight average molecular weight Mw of the other polyorganosiloxane (s-1) was 6,000.

Example 1

&Lt; Preparation of liquid crystal aligning agent &

100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in Synthesis Example S1 and 1,000 parts by weight of the polyamic acid (pa-1) obtained in Synthesis Example pa- N-methyl-2-pyrrolidone and butyl cellosolve were added to the mixture, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) 3.0% by weight. This solution was filtered with a filter having an opening diameter of 1 占 퐉 to prepare a liquid crystal aligning agent.

&Lt; Production of liquid crystal display element &

A glass substrate having a metal electrode including chromium patterned in a comb shape on one side and an opposing glass substrate on which no electrode is provided are paired with each other to form a pair of surfaces having electrodes of the glass substrate and one surface of the opposing glass substrate The liquid crystal aligning agent (LA-1) prepared above was applied using a spinner, pre-baked for 1 minute on a hot plate at 80 DEG C, and then heated in an oven where the inside of the system was replaced with nitrogen at 200 DEG C for 1 hour Followed by baking) to form a coating film having a thickness of 0.1 mu m. Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; including a 313 nm bright line were irradiated from the direction of the substrate normal by using Hg-Xe lamps and Glan Taylor prisms respectively on the surface of these coating films to obtain a pair of substrates having liquid crystal alignment films .

An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer periphery of one surface of the substrate having the liquid crystal alignment film by screen printing and then the surfaces of the liquid crystal alignment films of the pair of substrates were opposed to each other, , And the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, liquid crystal MLC-7028 manufactured by Merck & Co., Inc. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then slowly cooled to room temperature. Subsequently, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other and orthogonal to the projection direction of the polarizing ultraviolet optical axis of the liquid crystal alignment film to the substrate surface, thereby producing a liquid crystal display element.

<Evaluation Method of Liquid Crystal Display Element>

The liquid crystal display device manufactured as described above was evaluated by the following method. The evaluation results are shown in Table 2.

(1) Evaluation of liquid crystal alignment property

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

(2) Evaluation of voltage holding ratio

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

Examples 2 to 12 and Comparative Examples 1 and 2

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the kind and amount of the polymers described in Table 2 were used as the radiation-sensitive polyorganosiloxane and the other polymers in Example 1, A liquid crystal display element was prepared and evaluated in the same manner as in Example 1 except that the irradiation amount of the polarized ultraviolet ray was changed as shown in Table 2. The evaluation results are shown in Table 2, respectively.

Further, in Example 7, two kinds of polymers were used in combination as another polymer in the production of the liquid crystal aligning agent.

Claims (4)

A radiation-sensitive polyorganosiloxane having at least one group selected from the group consisting of the groups represented by the following formulas (A1 ') and (A2'), and
At least one polymer selected from the group consisting of polyorganosiloxane, polyamic acid and polyimide other than the above-mentioned radiation-sensitive polyorganosiloxane
Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.
[Formula A1 ']

[Formula A2 ']

(Wherein R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, R ¹ is a phenylene group or a cyclohexylene group, provided that the hydrogen atom of the phenylene group or the cyclohexylene group R ² is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom, -CH = CH- or -NH-, and a part or all of R ¹ and R ² may be substituted with a fluorine atom or a cyano group, a is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ¹ and R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4 , "*" Indicates a binding hand;
In formula (A2 '), R' is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R ⁴ is a phenylene group or a cyclohexylene group, provided that the hydrogen atom all or part of may be substituted with a fluorine atom or a cyano group, R ⁵ is a single bond, methylene group, and having 2 or 3 alkylene group, an oxygen atom, a sulfur atom or -NH- in, c is 1 to 3 A plurality of R ⁴ and R ⁵ may be the same or different, R ⁶ is a fluorine atom or a cyano group, d is an integer of 0 to 4, R ⁷ is an oxygen An atom, -COO- + or -OCO - + (provided that the bonding hand having "+" is bonded to R ⁸ ), R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ⁹ represents a single _{bond, + -OCO- (CH 2) f} - or _{+ -O- (CH 2) g -} ( texture pasted on the "+" at the end, over Hand _{^{- (R 7 -R 8) e}} - side and, f and g is an integer of 1 to 10), and, e is an integer from 0 to 3, "*" denotes that the binding sonin) A method for forming a liquid crystal alignment film, comprising the steps of: applying a liquid crystal aligning agent according to claim 1 on a substrate to form a coating film; and irradiating the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent according to claim 1. The liquid crystal display element according to claim 3, wherein the liquid crystal display element is a transverse electrolytic method.