KR20100094955A - Liquid crystal aligning agent, process for forming liquid crystal aligning film, liquid crystal display device, and polyorganosiloxane - Google Patents

Abstract

PURPOSE: A liquid crystal aligning agent is provided to obtain good liquid crystal alignment through a photoalignment method when applied to a liquid crystal display device having a TN-type, STN-type, or IPS-type liquid cell and to be used for forming a liquid crystal alignment layer having excellent electrical properties. CONSTITUTION: A liquid crystal aligning agent contains: radiation-sensitive polyorganosiloxane having a functional group which is selected from chemical formula A1' and chemical formula A2'; and a polymer which is selected from a group comprising polyamic acid and polyimide. A method for forming a liquid crystal alignment layer includes a step of forming a coating layer by spreading the liquid crystal aligning agent on a liquid crystal alignment substrate and a step of irradiating radiation on the coating layer.

Description

Liquid crystal aligning agent, the formation method of a liquid crystal aligning film, a liquid crystal display element, and a polyorganosiloxane {LIQUID CRYSTAL ALIGNING AGENT, PROCESS FOR FORMING LIQUID CRYSTAL ALIGNING FILM, LIQUID CRYSTAL DISPLAY DEVICE, AND POLYORGANOSILOXANE}

This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.

Until now, TN (negative liquid crystal) having a positive dielectric anisotropy has a sandwich structure as a substrate with a transparent electrode having a liquid crystal alignment film, and the long axis of the liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates as necessary. Twisted Nematic (STN) type and STN (Super Twisted Nematic) type, IPS (In Plane Switching) type that applies an electric field in a direction parallel to the substrate by forming electrodes on one side of the substrate, and uses a nematic liquid crystal with negative dielectric anisotropy Liquid crystal display elements having various liquid crystal cells such as VA (Vertical Alignment) type 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 transverse electrolytic liquid crystal display element.

In such a liquid crystal cell, in order to orient liquid crystal molecules with respect to the substrate surface in a predetermined direction, a liquid crystal alignment film is provided on the substrate surface. In the liquid crystal cells of TN type, STN type, and IPS type, this liquid crystal aligning film is formed by the method (rubbing method) which rubs the surface of the organic film formed in the surface of the board | substrate in one direction with the cloth member, such as rayon normally. However, when the liquid crystal alignment film is formed by a rubbing process, dust and static electricity are easily generated during the rubbing process, and thus, there is a problem that dust adheres to the surface of the alignment film and causes display defects, as well as TFT (Thin Film Transistor). In the case of a substrate having a device), circuit breakage of the TFT device occurs due to the generated static electricity, which causes a decrease in product yield. Moreover, in the liquid crystal display element which tends to become more accurate in the future, uniform rubbing process becomes difficult because of the unevenness | corrugation which inevitably arises in the surface of a board | substrate with the densification of a pixel.

Therefore, as another means for orienting a liquid crystal in a liquid crystal cell, a photo-alignment method for imparting liquid crystal alignment capability by irradiating polarized or non-polarized radiation to a photosensitive organic thin film formed on a substrate surface has been proposed (Patent Documents 5 to 5). 15). According to this technique, it is possible to realize uniform liquid crystal alignment without generating static electricity or dust. This technique can be applied to VA type liquid crystal cells in addition to TN type, STN type and IPS type liquid crystal cells.

It is reported that the liquid crystal aligning film which has favorable electric characteristic is obtained by the photo-alignment method in recent years by using a specific azo compound in the liquid crystal aligning agent used for a TN type liquid crystal cell (patent document 16). However, according to this technique, since the accumulated exposure amount of 10,000 J / m 2 or more is required for the formation of the liquid crystal alignment film, the degree of damage over time of the exposure apparatus is large, and the cost of manufacturing the liquid crystal alignment film becomes expensive. It is implicated.

Moreover, it is reported that the liquid crystal aligning agent containing the polymer which has a specific long-chain structure or cyclic structure provides the liquid crystal aligning film excellent in liquid crystal aligning property and electrical characteristics by the photo-alignment method of the low exposure amount (patent documents 17-19). This technique is an excellent technique for easily and inexpensively forming a liquid crystal alignment film having a desired performance when applied to a liquid crystal display device having a VA type liquid crystal cell, but a liquid crystal having a liquid crystal cell of a TN type, STN type or IPS type. When applied to a display element, the liquid crystal alignment is not necessarily sufficient.

When applied to a liquid crystal display element having a liquid crystal cell of TN type, STN type or IPS type, in particular, an IPS type liquid crystal display element, a liquid crystal alignment film having excellent liquid crystal alignment property and electrical properties can be provided by a light exposure method with a small exposure amount. Liquid crystal aligning agents are not yet known.

Japanese Patent Laid-Open No. 56-91277 Japanese Patent Laid-Open No. 1-20528 US Patent No. 5,928,733 Japanese Patent Laid-Open No. 11-258605 Japanese Patent Publication No. 6-287453 Japanese Patent Publication No. 10-251646 Japanese Patent Publication No. 11-2815 Japanese Patent Laid-Open No. 11-152475 Japanese Patent Laid-Open No. 2000-144136 Japanese Patent Laid-Open No. 2000-319510 Japanese Patent Laid-Open No. 2000-281724 Japanese Patent Publication No. 9-297313 Japanese Patent Laid-Open No. 2003-307736 Japanese Patent Laid-Open No. 2004-163646 Japanese Patent Publication No. 2002-250924 Japanese Patent Laid-Open No. 2007-138138 International Publication No. 2009/025385 International Publication No. 2009/025386 International Publication No. 2009/025388 Japanese Patent Laid-Open No. 63-291922

 Chemical Reviews, 95, p. 1409 (1995)

This invention is made | formed in view of the said situation, When the objective is applied to the liquid crystal display element which has a liquid crystal cell of a TN type, STN type, or IPS type, it shows the favorable liquid crystal aligning ability by the optical alignment method by a small exposure amount, It is providing the liquid crystal aligning agent which can form the liquid crystal aligning film excellent in various performances, such as an electrical property.

Another object of this invention is to provide the liquid crystal aligning film and liquid crystal display element which have the outstanding characteristic as mentioned above.

Still 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, firstly,

It is achieved by the liquid crystal aligning agent containing the radiation-sensitive polyorganosiloxane which has 1 or more types chosen from the group which consists of group represented by each of following General formula A1 'and A2'.

[Formula A1 ']

[Formula A2 ']

In formula A1 ', R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R ¹ is a phenylene group or a cyclohexylene group, provided that a hydrogen atom of the phenylene group or cyclohexylene group is used. Some or all of may be substituted with a fluorine atom or a cyano 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-, a is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ¹ and R ^{2 present} 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 "*" Represents a bond;

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 a hydrogen atom of the phenylene group or cyclohexylene group is used. Some or all of may be substituted with a fluorine atom or a cyano group, R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, and c is 1 to 3 An integer, and when c is 2 or 3, a plurality of R ⁴ and R ^{5 present} may be the same or different, R ⁶ is a fluorine atom or a cyano group, d is an integer of 0 to 4, and R ⁷ is oxygen An atom, -COO- + or -OCO- +, provided that the bond to which "+" is attached is combined with R ^8, and 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 secondly achieved by a liquid crystal alignment film formed of the above liquid crystal aligning agent,

Third, it is achieved by a liquid crystal display device having the above liquid crystal alignment film.

When the liquid crystal aligning agent of this invention is applied to the liquid crystal display element which has a TN type, STN type, or IPS type liquid crystal cell, especially the transverse electrolytic type liquid crystal display element which has a liquid crystal cell of IPS type, the photo-alignment method by a small exposure amount It is possible to form a liquid crystal alignment film that exhibits good liquid crystal alignment ability and is excellent in various performances such as electrical properties.

Since the liquid crystal display element of this invention provided with the liquid crystal aligning film formed from such a liquid crystal aligning agent of this invention is possible to display high quality, and it is inexpensive, it can be effectively applied as various display apparatuses.

The liquid crystal aligning agent of this invention contains the radiation sensitive polyorganosiloxane which has 1 or more types chosen from the group which consists of groups represented by said general formula A1 'and A2', respectively.

<Radiation Polyorganosiloxane>

The radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention has one or more types chosen from the group which consists of groups represented by said general formula A1 'and A2', respectively.

As the alkyl group having 1 to 3 carbon atoms of R in the general formula (A1 ') and R' in the general formula (A2 '), a methyl group, an ethyl group, or an n-propyl group is preferable, respectively. It is preferable that the phenylene group and cyclohexylene group of R <^1> in said Formula (A1 ') and R <^4> in said Formula (A2') are a ^1, 4- phenylene group or a 1, 4- cyclohexylene group, respectively.

As R <^2> in the said general formula (A1 '), it is preferable that they are a single bond, an oxygen atom, or -CH = CH-.

As a bivalent aromatic group of R <^8> in the said General formula A2 ', For example, 1, 4- phenylene group, 4, 4'- biphenylene group, etc .;

As a bivalent alicyclic group, a 1, 4- cyclohexylene group, a 4,4'-bicyclohexylene group, etc. are mentioned, for example;

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

Examples of the divalent condensed cyclic group include anthraquinone-2,6-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl and naphthalene-2. , 7-diyl group, anthracene-9,10-diyl group, carbazole-3,6-diyl group, dibenzothiophene-2,8-diyl group and the like. In Formula A2 ', e is preferably 0.

As a specific example of the group which the radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention has, the group represented by each of following formula is mentioned as group represented by said Formula (A1 ');

(However, "*" indicates that the bond is)

As group represented by the said Formula (A2 '), group represented by each of following formula is mentioned, for example.

(However, "*" indicates that the bond is)

The content rate of the 1 or more types chosen from the group which consists of groups represented by said general formula A1 'and A2' in the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention is 0.2-6 mmol / g It is preferable that it is a polymer, and it is more preferable that it is 0.3-5 mmol / g-polymer.

It is preferable that the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention has an epoxy group in addition to 1 or more types chosen from the group which consists of groups represented by said general formula A1 'and A2', respectively. 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 even more preferably 200 to 2,000 g / mol. By using the epoxy equivalent radiation-sensitive polyorganosiloxane in such a ratio, the liquid crystal aligning agent of this invention forms the liquid crystal aligning film which was more excellent in liquid crystal orientation and excellent in afterimage characteristics, without impairing the storage stability of a liquid crystal aligning agent. It is preferable because it becomes possible.

About the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention, it is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography is 1,000-200,000, It is more preferable that it is 2,000-100,000 In particular, it is preferable that they are 3,000-30,000.

<Synthesis of radiation sensitive polyorganosiloxane>

The radiation-sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention may use what was synthesize | combined by any method as long as it is as above-mentioned. As a synthesis | combining method of the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention, for example,

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

It can carry out by the method etc. which make the polyorganosiloxane which has an epoxy group, and 1 or more types chosen from the group which consists of a compound represented by each of following General formula A1 and A2 react.

[Formula A1]

[Formula 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 ′, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , c, d and e in Formula A2 have the same meanings as in Formula A2 ′, respectively)

Among these, it is preferable by the latter method from a viewpoint of the ease of synthesis of a raw material compound, the ease of reaction, etc.

Hereinafter, it is selected from the group which consists of the polyorganosiloxane which has an epoxy group which is a preferable method for synthesize | combining the radiation sensitive polyorganosiloxane contained in the liquid crystal aligning agent of this invention, and the compound represented by said Formula (A1) and A2, respectively. One or more reaction methods to be described are demonstrated.

[Polyorganosiloxane with Epoxy]

The epoxy group in the polyorganosiloxane having an epoxy group is a group in which an ethylene oxide skeleton or a 1,2-epoxycycloalkane skeleton is bonded to a silicon atom directly or through an alkylene which may be interrupted by an oxygen atom ( It is preferable to exist in polyorganosiloxane as contained in the group which has an epoxy group. As group which has such an epoxy group, group represented by following General formula (EP-1) or (EP-2) is mentioned, for example.

(In formula (EP-1) and (EP-2), "*" shows a bond.)

The epoxy equivalent of the polyorganosiloxane which has an epoxy group becomes like this. Preferably it is 100-10,000 g / mol, More preferably, it is 150-1,000 g / mol.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography with respect to the polyorganosiloxane which has an epoxy group is 500-100,000, It is more preferable that it is 1,000-10,000, It is especially preferable that it is 1,000-5,000. .

The polyorganosiloxane having such an epoxy group is, for example, hydrolyzed and condensed with a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. It can synthesize | combine by making it.

As a silane compound which has the said epoxy group, 3-glycidyloxy propyl trimethoxysilane, 3-glycidyl oxypropyl triethoxy silane, 3-glycidyl oxypropyl methyl dimethoxy silane, 3-glycol, for example Cydyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane etc. are mentioned.

As said other silane compound, for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyl Tri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorocysilane, 2- (triple Oromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri -i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n- Hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n- Hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane , 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltri Methoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane,

2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl ) Ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimeth Methoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- ( (Meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane , 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3 Mercaptopropyl tree Chlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3 -Mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyl Trimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichloro Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxy Column, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxy Silane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxy Silane, dimethyldi-sec-butoxysilane,

(Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro R-n-octyl) ethyl] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-i-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) die Methoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di -n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) Diethoxysilane, (methyl) (vinyl) di-n-prop Foxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, Divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxy Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, di Phenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-pro Foxtrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethyl Column, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) In addition to the silane compound which has one silicon atom, such as diphenylsilane,

As a brand name, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X- 22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40- 2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, manufactured by Shin-Etsu Chemical Co., Ltd.); Glass resin (manufactured by Showa Denko Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Corporation); FZ3711 and FZ3722 (above, manufactured by Nippon Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, and XMS-5025 (above, manufactured by Chisso Corporation); Methyl silicate MS51 and methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcot Co., Ltd.); Partial condensates, such as GR100, GR650, GR908, GR950 (above, Showa Denko Co., Ltd.), can be mentioned, One or more of these can be used.

As another silane compound, tetramethoxysilane, tetraethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryl among the above-mentioned things Oxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimeth Using at least one member selected from the group consisting of oxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane It is preferable.

When synthesize | combining the polyorganosiloxane which has an epoxy group in this invention, it is preferable to manufacture and set so that the epoxy equivalent of the polyorganosiloxane which obtains the use ratio of the silane compound which has an epoxy group and another silane compound may be in the above-mentioned preferable range. Do.

As an organic solvent which can be used when synthesize | combining the polyorganosiloxane which has an epoxy group, a hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example.

As said hydrocarbon, toluene, xylene, etc. are mentioned, for example; As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc .;

As said ester, For example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .;

As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .;

Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. It is preferable that they are water-insoluble among these.

These organic solvents can be used individually or in mixture of 2 or more types.

The amount of the organic solvent to be used is preferably 10 to 10,000 parts by weight, more preferably 100 parts by weight of the total of the silane compounds (the total of the silane compound having an epoxy group and the other silane compound optionally used, which is the same below). Preferably 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, based on 1 mole of the total of the silane compounds.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. can be used, for example.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc. are mentioned, for example.

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, diazabicycloundecene; And quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As a catalyst at the time of synthesize | combining the polyorganosiloxane which has 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, the desired polyorganosiloxane can be obtained at a fast hydrolysis and condensation rate without causing side reactions such as ring opening of an epoxy group, and thus it is preferable because the production stability is excellent. . Moreover, the liquid crystal aligning agent of this invention containing the reaction material of the polyorganosiloxane which has the epoxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst and cinnamic acid derivative is preferable since it is very excellent in storage stability. The reason for this is that, as pointed out in Non-Patent Document 1 (Chemical Reviews, 95, p. 1409 (1995)), random structures are used when an alkali metal compound or an organic base is used as a catalyst in hydrolysis and condensation reactions. , A ladder structure or a cage structure is formed, and it is presumed that it is because the polyorganosiloxane with little content rate of a silanol group is obtained. Condensation reaction of silanol groups is suppressed because the content ratio of silanol groups is small, and when the liquid crystal aligning agent of this invention contains another polymer mentioned later, condensation reaction of a silanol group and another polymer is suppressed, and it is storage stability It is assumed that this is an excellent result.

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

Hydrolysis and condensation reaction when synthesizing a polyorganosiloxane having an epoxy group include dissolving a silane compound having an epoxy group and another silane compound in an organic solvent, if necessary, and mixing the solution with an organic base and water. For example, it is preferable to carry out by heating using suitable heating apparatuses, such as an oil bath.

In the case of the hydrolysis and condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., preferably 0.5 to 12 hours, more preferably 1 to 8 hours. . During heating, the mixed liquid may or may not be stirred, or the mixed liquid 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 washing | cleaning, washing | cleaning operation becomes easy by wash | cleaning with water containing a small amount of salts, for example about 0.2 weight% of ammonium nitrate aqueous solution, etc., and is preferable. The washing is performed until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a suitable drying agent such as calcium sulfate anhydride and molecular sieve, if necessary, and then the solvent is removed to remove the polyorganosiloxane having a target epoxy group. Can be obtained.

In this invention, what is marketed can also be used as polyorganosiloxane which has an epoxy group. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Tosoh Co., Ltd. product) etc. are mentioned, for example.

[Compound represented by each of Formulas A1 and A2]

As a specific example of the compound represented by said general formula (A1) and A2, the carboxylic acid formed by bonding a hydrogen atom to the bond of the group illustrated above as group represented by each of said general formula (A1 ') and A2' can be mentioned.

[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 the above formulas A1 and A2, respectively. It can be obtained easily by making 1 or more types react preferably in presence of a catalyst and an organic solvent.

Here, at least one selected from the group consisting of compounds represented by the above formulas A1 and A2 is preferably 0.001 to 10 mol, more preferably 0.01 to 1 mol 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 said catalyst, a compound known as a so-called hardening accelerator which promotes reaction of an organic base or an epoxy compound and an acid anhydride can be used.

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, diazabicycloundecene;

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

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethylaminomethyl) phenol, cyclohexyl dimethylamine, and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methyldi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (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 adducts of isocyanuric acid adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine; Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

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

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

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

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

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type accelerator, such as a dicyandiamide, the addition product of an amine, and an epoxy resin;

Microcapsule-type latent curing accelerators in which a 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 accelerators;

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

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

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

The polyorganosiloxane which has an epoxy group, and 1 or more types of reaction chosen from the group which consists of a compound represented by each of said Formula (A1) and A2 can be performed in presence of an organic solvent as needed. As such an organic solvent, a hydrocarbon, an ether, ester, ketone, an amide, alcohol, etc. are mentioned, for example. Of these, ethers, esters or ketones are preferred in view of solubility of raw materials and products and ease of purification of the products. The solvent is used at a ratio such that the solid content concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably at least 0.1% by weight, more preferably 5 to 50% by weight.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

Synthesis of the radiation-sensitive polyorganosiloxane as described above is one or more selected from the group consisting of groups represented by the general formulas A1 'and A2' by the ring-opening addition of the epoxy of the polyorganosiloxane having an epoxy group It is a method of introducing a group. This synthesis method is simple and is a very preferred method in that the introduction ratio of at least one group selected from the group consisting of groups represented by the above formulas A1 'and A2' can be increased.

<Other Ingredients>

The liquid crystal aligning agent of this invention contains the radiation sensitive polyorganosiloxane as mentioned above.

In addition to the radiation sensitive polyorganosiloxane as mentioned above, the liquid crystal aligning agent of this invention may contain another component, unless the effect of this invention is impaired. As such other components, for example, a polymer other than radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polymer"), a curing agent, a curing catalyst, a curing accelerator, a compound having one or more epoxy groups in the molecule (except persimmon) Except those corresponding to radioactive polyorganosiloxanes, hereinafter referred to as "epoxy compounds", functional silane compounds (except those corresponding to radiation-sensitive polyorganosiloxanes), surfactants, etc. Can be.

[Other polymers]

The said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical characteristic of the obtained liquid crystal aligning film further. As such another polymer, for example, at least one polymer selected from the group consisting of polyamic acid and polyimide, polyorganosiloxanes other than the radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polyorganosiloxane") ), Polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.

{Polyamic acid}

The said polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react.

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid in this invention, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Can be. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro -3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6 -Dianhydrides, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6- dianhydrides, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride etc. can be mentioned, respectively,

The tetracarboxylic dianhydride described in patent documents 17-19 can be used.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to contain alicyclic tetracarboxylic dianhydride among these, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, and 1, It is more preferable to include 1 or more types chosen from the group which consists of 2,3, 4- cyclobutane tetracarboxylic dianhydride, It is preferable to contain 2,3, 5- tricarboxy cyclopentyl acetic dianhydride especially. Do.

As tetracarboxylic dianhydride used for synthesizing the polyamic acid, the group consisting of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride It is preferable to contain 10 mol% or more with respect to all the tetracarboxylic dianhydrides, More preferably, it contains 20 mol% or more, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride contains 1 or more types chosen from the above. It is most preferable to include only 1 or more types chosen from the group which consists of water and 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

As diamine used for synthesize | combining a polyamic acid, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As an aliphatic diamine, For example, 1, 1-methacrylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-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-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5- Diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholesterol, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1 , 1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-hep Ylcyclohexyl) cyclohexane and the compound represented by the following general formula (D-1);

(In Formula (D-1), X ^I represents an alkyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OCO-, provided that a bond with "*" is bonded to the diaminophenyl group.) ), H is 0 or 1, i is an integer from 0 to 2, j is an integer from 1 to 20)

As diamino organosiloxane, not only 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc. are mentioned, respectively,

The diamine described in patent documents 17-19 can be used.

X ^I in the formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, * -O- or * -COO-, provided that the bond to which "*" is attached is combined with a diaminophenyl group. . Group C _j H _{2j + 1} - a concrete example, for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4- or 3, 5-position with respect to another group.

As a specific example of a compound represented by the said General formula (D-1), the compound etc. which are respectively represented by following General formula (D-1-1)-(D-1-4) are mentioned, for example.

In the formula (D-1), h and i are preferably not zero at the same time.

These diamines can be used individually or in combination of 2 or more types.

As for the ratio of use of the tetracarboxylic dianhydride and diamine used for the synthesis reaction of a polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of amino group contained in a diamine compound, More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably at a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably 2 to 10 hours. Is done during. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N Aprotic polar solvents such as, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphotriamide;

Phenolic solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, etc. are mentioned. The amount (a) of the organic solvent used is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (b) of the tetracarboxylic dianhydride and the diamine compound. It is the quantity used as 30 weight%.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for

When the polyamic acid is dehydrated and closed to give a polyimide, the reaction solution may be used as it is for the dehydration ring-closure reaction, or the polyamic acid contained in the reaction solution may be isolated and then used for the dehydration ring-closure reaction, or the isolated polyamic acid. After purification, it can be used for dehydration ring closure reaction.

Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or distilling off the organic solvent in a reaction solution by evaporation under reduced pressure. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or performing a process of distillation under reduced pressure with an evaporator once or several times.

{Polyimide}

The polyimide can be synthesized by dehydrating and closing the amic acid structure of the polyamic acid obtained as described above. At this time, all the amic acid structures may be dehydrated and completely imidized, or only a part of the amic acid structures may be dehydrated and closed to be a partial imide in which the amic acid structure and the imide structure coexist.

The dehydration ring closure of the polyamic acid may be carried out by (i) a method of heating the polyamic acid, or (ii) by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. I can do it.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. 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, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of polyamic-acid structural units. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the obtained polyimide. On the other hand, in the said method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution, and for the production of the liquid crystal aligning agent after isolating polyimide. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as mentioned above as a method of isolation and purification of a polyamic acid.

{Other Polyorganosiloxanes}

The other polyorganosiloxane in this invention is polyorganosiloxane other than the above-mentioned radiation-sensitive polyorganosiloxane. Such other polyorganosiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as "raw material silane compound"), preferably in a suitable organic solvent, water And hydrolysis and condensation in the presence of a catalyst.

As a raw material silane compound used here, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-part Methoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltri-iso-propoxysilane, Methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, Methyltri -tert-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyl tree -n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc. are mentioned, It is preferable to use 1 or more types of these, Especially, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyl tri Preference is given to using at least one selected from the group consisting of ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane. .

The other polyorganosiloxane in this invention can be synthesize | combined similarly to what was mentioned above as a synthesis | combining method of the polyorganosiloxane which has an epoxy group except using the raw material silane compound as mentioned above.

It is preferable that it is 1,000-100,000, and, as for the other polyorganosiloxane, the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography is more preferable.

{Rate of use of other polymers}

When the liquid crystal aligning agent of this invention contains another polymer with the radiation sensitive polyorganosiloxane mentioned above, it is 10,000 weight part or less with respect to 100 weight part of radiation sensitive polyorganosiloxane as a use ratio of another polymer. desirable. The more preferable use ratio of another polymer differs according to the kind of other polymer.

The more preferable use ratio of both when the liquid crystal aligning agent of this invention contains 1 or more types of polymers chosen from the group which consists of a radiation sensitive polyorganosiloxane, a polyamic acid, and a polyimide is a radiation sensitive polyorgano. 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, the more preferable use ratio of the case where the liquid crystal aligning agent of this invention contains a radiation sensitive polyorganosiloxane and another polyorganosiloxane is another poly with respect to 100 weight part of radiation sensitive polyorganosiloxanes. The amount of organosiloxane is from 100 to 2,000 parts by weight.

When the liquid crystal aligning agent of this invention contains another polymer with a radiation sensitive polyorganosiloxane, As another kind of polymer, 1 or more types of polymers or other polyorgano which are chosen from the group which consists of a polyamic acid and a polyimide It is preferred that they are siloxane or both.

Curing Agents and Curing Catalysts

The curing agent and curing catalyst may be contained in the liquid crystal aligning agent of the present invention for the purpose of further strengthening the crosslinking reaction of the radiation-sensitive polyorganosiloxane, the curing accelerator for the purpose of promoting the curing reaction that the curing agent is responsible for It may be contained in the liquid crystal aligning agent of this invention.

As said hardening | curing agent, the hardening | curing agent generally used for hardening of the curable composition containing the curable compound which has an epoxy group, or the compound which has an epoxy group can be used, For example, polyhydric amine, polyhydric carboxylic anhydride, polyhydric carboxylic acid is illustrated. can do.

As said polyhydric carboxylic anhydride, the anhydride of cyclohexane tricarboxylic acid and other polyhydric carboxylic anhydride are mentioned, for example.

As a specific example of cyclohexane tricarboxylic anhydride, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, cyclohexane-1,3,5-tricarboxylic acid-3, 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydride, etc. are mentioned, As other polyhydric carboxylic acid anhydride, 4-methyltetrahydrophthalic anhydride, methyl, for example. Tetracarboxylic dianhydride generally used for the synthesis of nadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, compounds represented by the following general formula (CA-1) and polyamic acid In addition to water, the alicyclic compound which has conjugated double bonds, such as (alpha)-terpinene and allocymen, maleic anhydride Diels-Alder reaction product, these hydrogenated products, etc. are mentioned.

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

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

As said hardening accelerator, it is an imidazole compound, for example;

Quaternary phosphorus compounds;

Quaternary amine compounds;

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

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

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

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

Microcapsule-type latent curing accelerators wherein surfaces such as quaternary phosphonium salts are coated with a polymer;

Amine salt type latent curing accelerators;

High temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

Epoxy Compound

The said epoxy compound can be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning film formed.

As such an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl -Aminomethylcyclohexane etc. are mentioned as a preferable thing.

When the liquid crystal aligning agent of this invention contains an epoxy compound, Preferably it is 40 weight part or less with respect to a total of 100 weight part of said radiation-sensitive polyorganosiloxane and the other polymer arbitrarily used, More preferably, it is 0.1-30 weight part.

Moreover, when the liquid crystal aligning agent of this invention contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, in order to raise the crosslinking reaction efficiently.

[Functional silane compound]

The said functional silane compound can be used for the purpose of improving the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. As a functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, 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 Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-amino Lofiltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N -Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The reactant of tetracarboxylic dianhydride and the silane compound which has an amino group as described in patent document 20 (Unexamined-Japanese-Patent No. 63-291922), etc. can be used.

When the liquid crystal aligning agent of this invention contains a functional silane compound, As the content rate, Preferably it is 50 weight part or less with respect to a total of 100 weight part of said radiation-sensitive polyorganosiloxane and the other polymer used arbitrarily. More preferably, it is 20 weight part or less.

[Surfactants]

As said surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

When the liquid crystal aligning agent of this invention contains surfactant, it is 10 weight part or less with respect to all 100 weight part of liquid crystal aligning agents as the content rate, More preferably, it is 1 weight part or less.

<Liquid crystal aligning agent>

Although the liquid crystal aligning agent of this invention contains a radiation sensitive polyorganosiloxane as an essential component as mentioned above, and contains other components as needed in addition, Preferably, each component dissolved in the organic solvent phase It is prepared as a composition.

As an organic solvent which can be used for manufacturing the liquid crystal aligning agent of this invention, it is preferable to melt | dissolve a radiation sensitive polyorganosiloxane and other components used arbitrarily, and to not react with these.

The organic solvent which can be preferably used for the liquid crystal aligning agent of this invention changes with kinds of the other polymer added arbitrarily.

When the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane and polyamic acid and polyimide, and radiation-sensitive polyorganosiloxane and polyamic acid and polyimide As a preferable organic solvent in the case of containing another polyorganosiloxane other than 1 or more types of polymers chosen from the group which consists of these, the organic solvent illustrated above as what is used for synthesis | combination of a polyamic acid is mentioned. At this time, the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention can also be used together. These organic solvents can be used individually or in combination of 2 or more types.

On the other hand, when the liquid crystal aligning agent of this invention contains only radiation-sensitive polyorganosiloxane as a polymer, or contains radiation-sensitive polyorganosiloxane and other polyorganosiloxane, the group which consists of polyamic acid and polyimide As a preferable organic solvent in the case of not containing 1 or more types of polymers chosen from, for example, 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Butyl ether (butyl cell Sorb), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol , Propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate And methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, etc. are mentioned preferably.

The preferable solvent used for manufacture of the liquid crystal aligning agent of this invention is obtained by combining 1 type (s) or 2 or more types of the above-mentioned organic solvent according to the presence or absence of the use of another polymer, and its kind, and liquid-crystal orientation in the following preferable solid content concentration Each component contained in the agent does not precipitate, and the surface tension of the liquid crystal aligning agent is in a range of 25 to 40 mN / m.

Solid content concentration of the liquid crystal aligning agent of this invention, ie, the ratio which the weight of all components other than the solvent in a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Preferably it is 1-10 weight It is% of range. Although the liquid crystal aligning agent of this invention forms the coating film used as a liquid crystal aligning film by apply | coating to the surface of a board | substrate, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and it may be difficult to obtain a favorable liquid crystal aligning film. . On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and it is difficult to obtain a favorable liquid crystal aligning film, the viscosity of a liquid crystal aligning agent may increase, and coating characteristics may be inadequate. The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially preferable. In the case of the printing method, it is particularly preferable that the solid content 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. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 0 degreeC-40 degreeC.

<Formation Method of Liquid Crystal Alignment Film>

The liquid crystal aligning agent of this invention uses the photo-alignment method to the liquid crystal aligning film used for the liquid crystal display element which has a liquid crystal aligning film, a TN type, or STN type liquid crystal cell, or the transverse electrolytic system liquid crystal display element which has a liquid crystal cell of IPS type. It may be preferably used to form. Since the liquid crystal aligning agent of this invention exhibits the effect of this invention to the maximum when it applies especially to the liquid crystal display element which has a liquid crystal cell of IPS type, it is preferable.

In order to form a liquid crystal aligning film using the liquid crystal aligning agent of this invention, it can carry out by the method of apply | coating the liquid crystal aligning agent of this invention on a board | substrate, forming a coating film, and passing the process of irradiating a radiation to the said coating film.

Here, when applying the liquid crystal aligning agent of this invention to the liquid crystal display element which has a TN type or STN type liquid crystal cell, two board | substrates with which the patterned transparent conductive film is provided are paired, and each transparent conductive film formation is carried out The liquid crystal aligning agent of this invention is apply | coated on the surface, and a coating film is formed. On the other hand, when applying the liquid crystal aligning agent of this invention to the liquid crystal display element which has a liquid crystal cell of an IPS type | mold, the board | substrate which has an electrode in which the transparent conductive film or the metal film was patterned in the shape of the comb teeth on one side, and the electrode are not provided Using a pair of non-facing substrates, the liquid crystal aligning agent of this invention is apply | coated to the formation surface of a comb-tooth shaped electrode, and one side of an opposing board | substrate, respectively, and a coating film is formed.

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

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

Application of the liquid crystal aligning agent onto the substrate is preferably carried out by an appropriate coating method such as an offset printing method, spin coating method, roll coater method, inkjet printing method, and the like, followed by preheating (prebaking) the coated surface. The coating film is formed by baking (post-baking). The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-baking conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably Preferably 10 to 100 minutes. The film thickness of the coating film after post-baking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The liquid crystal aligning ability is provided by irradiating linearly or partially polarized radiation or unpolarized radiation to the coating film formed in this way. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an inclined direction in order to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of irradiation needs to be inclined direction.

As a light source to be used, 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, etc. can be used, for example. Ultraviolet rays in the preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

The irradiation amount of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, more preferably 10 to 3,000 J / m 2. Moreover, when providing the liquid-crystal aligning ability to the coating film formed from the liquid crystal aligning agent known conventionally by the photo-alignment method, the radiation amount of 10,000 J / m <2> or more was needed. However, when the liquid crystal aligning agent of this invention is used, even if the radiation dose at the time of photo-alignment method is 3,000 J / m <2> or less, Furthermore, 1,000 J / m <2> or less can provide favorable liquid-crystal orientation ability, and the productivity of a liquid crystal display element is improved. It is effective for reducing the manufacturing cost.

<Method of Manufacturing Liquid Crystal Display Element>

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

First, a pair of board | substrates with which the liquid crystal aligning film was formed as mentioned above is prepared, and the liquid crystal cell of the structure by which the liquid crystal was clamped between this pair of board | substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are disposed to face each other so as to face each liquid crystal alignment film, and the peripheral portions of the two substrates are bonded together using a sealant, and the cell partitioned by the substrate surface and the sealant. After the injection filling of the liquid crystal within the interval, the liquid crystal cell can be produced by sealing the injection hole.

The second method is a method called an ODF (One Drop Fill) method. An ultraviolet photocurable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent.

In any case, it is preferable to remove the liquid crystal filling during liquid crystal filling by gradually cooling the liquid crystal cell to a temperature at which the used liquid crystal takes an isotropic phase and then gradually cooling to room temperature.

Moreover, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. Here, a desired liquid crystal display element can be obtained by adjusting the angle which the polarization direction of the irradiated linearly polarized radiation and the angle of each board | substrate and a polarizing plate in two board | substrates with a liquid crystal aligning film formed suitably.

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

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example. It is preferable to have positive dielectric anisotropy which forms a nematic type liquid crystal, For example, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal , Dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cuban-based liquid crystal and the like are used. Moreover, for the said liquid crystal, For example, cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonaate, cholesteryl carbonate;

Chiral agent sold as brand names "C-15" and "CB-15" (above, Merck);

Ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. are mentioned. .

The liquid crystal display element of this invention manufactured in this way is excellent in various performances, such as a display characteristic and an electrical characteristic.

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

The weight average molecular weight in the following synthesis examples is a polystyrene conversion value measured by the gel permeation chromatography of the following conditions, respectively.

Column: Toso Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68 kgf / ㎠

In addition, in the following synthesis examples, the synthesis | combination of a raw material compound and a polymer was repeated as needed on the following synthesis scale, and the required amount in the following Example was ensured.

<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 added to 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 dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, followed by distilling off the solvent and water under reduced pressure, thereby obtaining polyorganosiloxane (ES-). 1) was obtained as a viscous transparent liquid.

It was obtained as a poly organo the theoretical intensity peaks based on the subjected to ¹ H-NMR analysis of the siloxane bar, an epoxy group at the following chemical shifts (δ) = 3.2 ppm having an epoxy group, a side reaction of the epoxy group did not occur during the reaction Confirmed.

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

Synthesis Examples ES2 to 3

Except having made input material as shown in Table 1, it carried out similarly to the synthesis example 1, and obtained the polyorganosiloxane (ES-2) and (ES-3) which have an epoxy group as viscous transparent liquid, respectively.

Table 1 shows the Mw and epoxy equivalents of the polyorganosiloxanes having these epoxy groups.

In addition, in Table 1, abbreviated-name of a raw material silane compound is the following meanings, respectively.

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

MTMS: Methyltrimethoxysilane

PTMS: Phenyltrimethoxysilane

<Synthesis example of compound represented by Formula (A1)>

Compounds represented by the following general formulas (A1-1) to (A1-4) in the same manner as in Synthesis Examples A1-1 to A1-4 (hereinafter, respectively, "Compound (A1-1)" and "Compound (A1- 2) "," compound (A1-3) "and" compound (A1-4) ") were synthesized.

Synthesis Example A1-1

Into a 500 mL three-necked flask equipped with a cooling tube, 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 added thereto. It mixed and made into a solution. Subsequently, 7 g of acrylic acid was added to the solution using a syringe and stirred, followed by reaction at 120 ° C. for 3 hours with stirring. After confirming completion of the reaction by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. After filtering off the insoluble matter, the filtrate was poured into 300 mL of 1 N hydrochloric acid, and the precipitate was recovered. 8.4g of compounds (A1-1) were obtained by recrystallizing this precipitate from the mixed solvent (ethyl acetate: hexane = 1: 1 (volume ratio)) containing ethyl acetate and hexane.

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-bromocinnamic acid, 2.7 g of tetrakistriphenylphosphinepalladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran and pure water 39 mL was added and mixed, and reaction was performed at 80 degreeC under stirring for 8 hours. After completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature. The reaction mixture after cooling was poured into 200 mL of 1 N hydrochloric acid, and the precipitate was recovered. The solution obtained by dissolving the obtained precipitate in ethyl acetate was dried with anhydrous magnesium sulfate, washed sequentially with 100 mL of 1 N hydrochloric acid, 100 mL of pure water, and 100 mL of saturated saline solution, and then the solvent was distilled off. 9 g of compounds (A1-2) were obtained by vacuum drying the obtained solid.

Synthesis Example A1-3

In a 200 mL three-necked flask equipped with a cooling tube, 3.6 g of 4-fluorostyrene, 6 g of 4-bromocinnamic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine and dimethyl 50 mL of acetamide was added and mixed to prepare a solution. The solution was stirred at 120 ° C. for 3 hours to carry out the reaction. After confirming completion of the reaction by TLC, the reaction mixture was cooled to room temperature, the insolubles were separated by filtration, and the filtrate was poured into 300 mL of 1 N hydrochloric acid to recover the precipitate. 4.1g of compounds (A1-3) were obtained by recrystallizing this precipitate from ethyl acetate.

Synthesis Example A1-4

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

<Synthesis Example of Compound Represented by Formula A2>

Compounds represented by the following formulas (A2-1) and (A2-2), respectively, in the same manner as in Synthesis Examples A2-1 and A2-2 below (hereinafter, "Compound (A2-1)" and "Compound (A2- 2) ").

Synthesis Example A2-1

In a 200 mL three-necked flask equipped with a cooling tube, 10 g of phenylacrylate, 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 and dimethylacetamide 100 mL was added and mixed, and it was set as a solution. The solution was reacted with stirring at 120 ° C. for 3 hours. After confirming completion of the reaction by TLC, the reaction mixture was cooled to room temperature, the insolubles were separated by filtration, the filtrate was poured into 500 mL of 1 N hydrochloric acid, and the precipitate was recovered. This deposit was recrystallized from ethyl acetate, and 9.3 g of compounds (A2-1) were obtained.

Synthesis Example A2-2

Into a 200 mL three-necked flask equipped with a dropping funnel, 10 g of 4-cyclohexylphenol, 6.3 g of triethylamine, and 80 mL of dehydrated tetrahydrofuran were added and mixed. This was cooled in an ice bath, and a solution containing 5.7 g of acryloyl chloride and 40 mL of dehydrated tetrahydrofuran was added dropwise from the dropping funnel. After completion of the dropwise addition, the mixture was stirred for 1 hour under an ice bath, and then returned to room temperature, followed by reaction for 2 hours under stirring. After the reaction was completed, the reaction mixture was filtered and the resulting salt was removed. After washing the organic layer obtained by adding ethyl acetate to the filtrate, the solvent was removed under reduced pressure and 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 acrylic acid obtained above, 5.7 g of 2-fluoro-4-bromobenzoic acid, 0.06 g of palladium acetate, and tris (2-tolyl) 0.32 g of phosphine, 11 g of triethylamine, and 50 mL of dimethylacetamide were added and mixed to prepare a solution. The solution was reacted with stirring at 120 ° C. for 3 hours. After confirming completion of the reaction by TLC, the reaction mixture was cooled to room temperature, the insolubles were separated by filtration, the filtrate was poured into 300 mL of 1 N hydrochloric acid, and the resulting precipitate was recovered. 3.4g of compounds (A2-2) were obtained by recrystallizing this deposit from ethyl acetate.

<Comparative Synthesis Example of Carboxylic Acid>

Synthesis Example RA1

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

In a 500 mL three-necked flask equipped with a cooling tube, 6.2 g of ethyl chalconyloxyacetate obtained above, 2 g of sodium hydroxide, 200 mL of ethanol, and 50 mL of water were added and mixed, and the reaction was performed under reflux for 3 hours. . After completion of the reaction, the reaction mixture was cooled, acidified by adding dilute hydrochloric acid, and then extracted with 500 mL of ethyl acetate. After washing this with respect to the obtained organic layer, 4.1 g of compounds (compound (RA-1)) represented by following General formula (RA-1) were obtained by removing a solvent and drying it under reduced pressure.

<Synthesis example of radiation sensitive polyorganosiloxane>

Synthesis Example S1

3 g of compound (A1-1) obtained in Synthesis Example A1-1, 9.3 g of polyorganosiloxane (ES-1) having an epoxy group obtained in Synthesis Example ES1 in a 100 mL three-necked flask, 26 g of methyl isobutyl ketone And 0.10 g of UCAT 18X (trade name, quaternary amine salt manufactured by San Apro Co., Ltd.), and the reaction was carried out at 80 ° C. for 12 hours under stirring. After the completion of the reaction, the reaction mixture was poured into methanol, and the resulting precipitate was collected, dissolved in ethyl acetate to obtain a solution. The solution was washed three times, and then the solvent was distilled off to remove radiation-sensitive polyorganosiloxane ( 6.3 g of S-1) was obtained as a white powder. The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-1) was 3,500.

Synthesis Example S2

Radiation-sensitive polyorganosiloxane (S) in the same manner as in Synthesis Example S1 except that 3 g of Compound (A1-2) obtained in Synthesis Example A1-2 was used instead of Compound (A1-1) in Synthesis Example S1. 7.0 g of white powder of -2) was obtained. The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-2) was 4,900.

Synthesis Example S3

Radiation-sensitive polyorganosiloxane (S) in the same manner as in Synthesis Example S1 except that 4 g of Compound (A1-3) obtained in Synthesis Example A1-3 was used instead of Compound (A1-1) in Synthesis Example S1. 10 g of white powder of -3) was obtained. The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-3) was 5,000.

Synthesis Example S4

A radiation sensitive polyorganosiloxane (S) in the same manner as in Synthesis Example S1 except that 4 g of Compound (A1-4) obtained in Synthesis Example A1-4 was used instead of Compound (A1-1) in Synthesis Example S1. 10 g of a white powder of -4) were obtained. The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-4) was 4,200.

Synthesis Example S5

10.5 g of polyorganosiloxane (ES-2) having an epoxy group obtained in Synthesis Example ES2 instead of polyorganosiloxane (ES-1) having an epoxy group in Synthesis Example S1 was synthesized in place of compound (A1-1). 7.0 g of white powders of radiation-sensitive polyorganosiloxane (S-5) were obtained in the same manner as in Synthesis Example S1 except that 3.35 g of Compound (A2-1) obtained in Example A2-1 was used, respectively. The weight average molecular weight Mw of this radiation sensitive polyorganosiloxane (S-5) was 5,500.

Synthesis Example S6

Instead of polyorganosiloxane (ES-1) having an epoxy group in Synthesis Example S1, 11.4 g of polyorganosiloxane (ES-3) having an epoxy group obtained in Synthesis Example ES3 was synthesized in place of compound (A1-1). 9.6 g of a white powder of radiation-sensitive polyorganosiloxane (S-6) was obtained in the same manner as in Synthesis Example S1 except that 4.6 g of 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.

<Comparative Synthesis Example of Radiation-Resistant Polyorganosiloxane>

Synthesis Example RS1

Said synthesis example except having used compound 4.4g represented by following formula synthesize | combined according to the method of patent document 17 (international publication 2009/025385) instead of compound (A1-1) in the synthesis example S-1. In the same manner as in S1, 7.2 g of a white powder of 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

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

<Synthesis example of other polymer>

[Synthesis example of polyamic acid]

Synthesis Example pa1

19.61 g (0.1 mol) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2,2'-dimethylbiphenyl were added to 367.6 g of N-methyl-2-pyrrolidone. It melt | dissolved and reaction was performed at room temperature for 6 hours. The reaction mixture was poured into very excess methanol and the reaction product precipitated out. Methanol wash | cleaned this deposit, and it dried under reduced pressure at 40 degreeC for 15 hours, and 35g of polyamic acids (pa-1) were obtained.

Synthesis Example pa2

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 14.23 g (0.1 mol) of cyclohexanebis (methylamine) are dissolved in 329.3 g of N-methyl-2-pyrrolidone, and 60 The reaction was carried out at 占 폚 for 6 hours. The reaction mixture was poured into very excess methanol and the reaction product precipitated out. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 40 degreeC for 15 hours, and 32g of polyamic acids (pa-2) were obtained.

Synthesis Example of Polyimide

Synthesis Example pi-1

Take 17.5 g of polyamic acid pa-2 obtained in Synthesis Example pa-2, dissolve it in 232.5 g of N-methyl-2-pyrrolidone, add 3.8 g of pyridine and 4.9 g of acetic anhydride to 4 at 120 ° C. Dehydration ring-closure reaction was performed for time. After completion of the reaction, the reaction mixture was poured into very excess methanol to precipitate the reaction product. The precipitate was recovered, washed with methanol, and then 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 powders of other polyorganosiloxane (s-1) were obtained in the same manner as in Synthesis Example S1 except that 5 g of lauric acid was used instead of compound (A1-1) in Synthesis Example S1. The weight average molecular weight Mw of the said other polyorganosiloxane (s-1) was 6,000.

Example 1

<Production of Liquid Crystal Alignment Agent>

1,000 parts by weight of polyamic acid (pa-1) obtained in Synthesis Example pa-1 as a polymer different from 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained as the radiation-sensitive polyorganosiloxane in Synthesis Example S1. The amount was added, and N-methyl-2-pyrrolidone and butyl cellosolve were added thereto, and the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio), and the solid content concentration was It was set as the solution which is 3.0 weight%. The liquid crystal aligning agent was manufactured by filtering this solution with the filter of 1 micrometer of pore diameters.

<Manufacture of Liquid Crystal Display Element>

A pair of glass substrates having a metal electrode containing chromium patterned in a comb-tooth shape on one side and an opposing glass substrate not provided with electrodes are provided on each side of the glass substrate and on one side of the opposing glass substrate. The above-mentioned liquid crystal aligning agent (LA-1) was apply | coated using a spinner, and it preliminarily baked on 80 degreeC hotplate for 1 minute, and then heated in 200 degreeC for 1 hour in oven which carried out the nitrogen substitution of the inside of the system ( Post-baking) to form a coating having a thickness of 0.1 탆. Subsequently, 300 J / m <2> of polarized ultraviolet-rays containing 313 nm bright line were irradiated to these coating-film surfaces using the Hg-Xe lamp and the Glan Taylor prism, respectively, and the pair of board | substrate which has a liquid crystal aligning film was obtained. .

After screen-printing the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer on the outer peripheral part of the surface which has one liquid crystal aligning film among the said board | substrates, the liquid crystal aligning film surface of a pair of board | substrate is made to oppose, and irradiate polarized ultraviolet-ray When it did, the board | substrate was overlapped and crimped | bonded so that the direction of the board | substrate might be reversed, and the adhesive agent was thermosetting at 150 degreeC over 1 hour. Subsequently, after filling a liquid crystal made by Merck and MLC-7028 in the clearance gap between a liquid crystal injection port and a board | substrate, the liquid crystal injection port was sealed with the epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, after heating to 150 degreeC, it cooled gradually to room temperature. Next, the liquid crystal display element was manufactured by bonding the polarizing plates to the outer both surfaces of a board | substrate so that the polarization directions may orthogonally cross, and orthogonally cross the projection direction to the board | substrate surface of the polarizing ultraviolet optical axis of a liquid crystal aligning film.

<Evaluation Method of Liquid Crystal Display Element>

The following method was evaluated about the liquid crystal display element manufactured above. The evaluation results are shown in Table 2.

(1) Evaluation of liquid crystal alignment

With respect to the liquid crystal display device manufactured above, the presence or absence of an abnormal domain in contrast change when the voltage of 5 V is turned on and off (applied and released) is observed by an optical microscope, and the abnormal domain is not observed. It was set as liquid crystal orientation "good", and the case where an abnormal domain was observed was evaluated as liquid crystal orientation "poor".

(2) Evaluation of voltage retention

A voltage of 5 V was applied to the liquid crystal display device manufactured as described above at 60 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica Corporation.

Examples 2-12 and Comparative Examples 1 and 2

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

In addition, in Example 7, two types of polymers were used together as another polymer at the time of manufacture of a liquid crystal aligning agent.

Claims (8)

A radiation-sensitive polyorganosiloxane having at least one group selected from the group consisting of groups represented by the formulas A1 'and A2', respectively, characterized in that it contains a liquid crystal aligning agent.
[Formula A1 ']

[Formula A2 ']

In formula A1 ', R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and R ¹ is a phenylene group or a cyclohexylene group, provided that a hydrogen atom of the phenylene group or cyclohexylene group is used. Some or all of may be substituted with a fluorine atom or a cyano 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-, a is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ¹ and R ^{2 present} 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 "*" Represents a bond;
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 a hydrogen atom of the phenylene group or cyclohexylene group is used. Some or all of may be substituted with a fluorine atom or a cyano group, R ⁵ is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, and c is 1 to 3 An integer, and when c is 2 or 3, a plurality of R ⁴ and R ^{5 present} may be the same or different, R ⁶ is a fluorine atom or a cyano group, d is an integer of 0 to 4, and R ⁷ is oxygen An atom, -COO- + or -OCO- +, provided that the bond to which "+" is attached is combined with R ^8, and 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 method according to claim 1, wherein the radiation-sensitive polyorganosiloxane is
Polyorganosiloxane which has an epoxy group,
A liquid crystal aligning agent which is at least one reaction product selected from the group consisting of compounds represented by the formulas A1 and A2, respectively.
[Formula A1]

[Formula 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 ′, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , c, d and e in Formula A2 have the same meanings as in Formula A2 ′, respectively) The liquid crystal aligning agent of Claim 1 or 2 which further contains 1 or more types of polymers chosen from the group which consists of a polyamic acid and a polyimide. The liquid crystal aligning agent of Claim 1 or 2 which further contains polyorganosiloxane other than the said radiation sensitive polyorganosiloxane. A method of forming a liquid crystal aligning film, comprising: applying a liquid crystal aligning agent according to claim 1 or 2 on a substrate to form a coating film and irradiating the coating film with radiation. The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 or 2 is provided. The liquid crystal display element characterized by the above-mentioned. The liquid crystal display device according to claim 6, wherein the liquid crystal display is a transverse electrolysis system. A polyorganosiloxane having at least one group selected from the group consisting of groups represented by each of Formulas A1 'and A2' according to claim 1.